PESTICIDE OR DETERRENT BASED ON GERANIOL AND CITRONELLAL

Description

[0001] The invention relates to a pesticidal or repellent active ingredient based on an unsaturated terpene compound chosen from geraniol and citronellal or a mixture of geraniol and citronellal, and more precisely to a combination of this (these) compound(s) with a surfactant and a solvent, as well as the uses of this active ingredient.

[0002] Geraniol is a constituent of rose, palmarosa, geranium, lemon, and citronella oils, from which it is extracted. It can also be obtained by chemical synthesis. Citronellal is a constituent of citronella and eucalyptus essential oils.

[0003] They are well-known and effective insecticides and insect repellents. They are widely used for these purposes, alone or in combination with one or more other active ingredients, preferably of natural origin.

[0004] Given their broad spectrum of action, geraniol and citronellal are present in many insecticides based on molecules derived from plant sources, and even if they remain effective in diluted form, as in aqueous solution, we are looking for effective insecticide compositions containing reduced levels of these said molecules. These are expensive products, such compositions would therefore be more economical. In addition, in their pure state, they present allergenic risks in the event of direct contact with the skin. New formulations allowing to reduce the concentrations of use are expected, both for the manufacturer and for the consumer. Furthermore, in certain cases, there is a need to significantly improve the speed or the rapidness of the action of geraniol, citronellal or the mixture of geraniol and citronellal.

[0005] According to EP3143876A1, an insecticidal active ingredient is known which combines geraniol and / or citronellal as the active substance and a glycol ether, making it possible to lower the effective levels of active substance, while leading to insecticidal performances superior to those of the active substance alone, on German cockroaches, the latter being representative of crawling insects in the efficacy tests.

[0006] There is still a need for compositions with a wider range of effectiveness and the ability to limit active substance levels.

[0007] It has been discovered, unexpectedly, that the combination of geraniol and / or citronellal as active substance, with an anionic and / or non-ionic and / or amphoteric surfactant on the one hand, and a solvent chosen from certain glycol ethers and ethyl lactate on the other hand, not only makes it possible to increase the insecticidal efficacy of the active substance compared to the active substance alone or in combination with a glycol ether according to EP3143876A1, but also to extend it more generally to a pesticidal or repellent efficacy, in the absence of any other chemical active substance, precisely in the absence of any other pesticidal substance, and for example pyrethroids. Although the invention and the entire description extend to amphoteric surfactants, a variant of the invention only uses one or more anionic surfactants, one or more non-ionic surfactants or mixtures of anionic surfactants and non-ionic surfactants.

[0008] Before discussing the description of the invention in more detail, certain terms used in this text are defined.

[0009] By pesticide, in any expression of the type pesticide substance, pesticide active ingredient, pesticide composition, pesticide effect, we mean the property consisting of destroying any organism considered harmful in a given environment. This term is generic and brings together insecticidal, fungicidal, herbicide, parasiticidal, bactericidal properties. In the context of the invention, the term pesticide applies in particular to the plant health or phytosanitary sector, and therefore to agriculture and horticulture, but also to the animal health or zoosanitary or veterinary sector for the treatment of farm or domestic animals, and also to any domestic or industrial sector.

[0010] An insecticide is understood to mean the property of killing crawling and flying insects, their larvae and eggs. For example, in addition to the well-known plant protection applications, an insecticide product may be used in a veterinary application as a pest control product, for the anti-lice treatment of livestock premises or for flea collars for dogs or cats, or in a domestic field, as a moth repellent, an ant repellent.

[0011] By repellent, in any expression of the type repellent substance, repellent active ingredient, repellent composition, repellent effect, we mean the effect of repelling organisms considered harmful in a given environment. In the context of the invention, the term repellent applies mainly to pests such as insects, pigeons, cats, dogs, but is not restricted to them.

[0012] Anionic surfactant is conventionally understood to mean an amphiphilic compound comprising a lipophilic part and a hydrophilic part, the latter being negatively charged. It has a Hydrophilic / Lipophilic Balance (HLB) of the order of 8 to 18. This definition essentially includes sulfonates such as paraffin sulfonates, sulfates such as alkyl(C1-C20)-sulfates and alkyl(C1-C20)-ether-sulfates, most commonly as salts, but not limited to, quaternary ammonium or any metal such as sodium. The term alkyl in this text refers to a saturated, linear or branched hydrocarbon group.

[0013] Secondary alkane sulfonate, also known as paraffin sulfonate (SAS for short), means a compound corresponding to the following formula: in which m and n are integers, identical or different, the sum of m and n being from 2 to 30, advantageously from 4 to 20, and better still from 10 to 14. Often, they are in the form of mixtures, we then speak of the average sum of m and n, this average sum of m and n ranging from 2 to 30, advantageously from 4 to 20, better still from 10 to 14. They are in the form of a salt such as sodium salt or any other compatible salt.

[0014] Examples of non-ionic surfactants which may be particularly used in the context of the invention include poly(ethylene glycol) derivatives, in particular alkyl poly(ethylene glycol) ethers in which the alkyl group is a linear or branched, saturated or unsaturated hydrocarbon chain having from 6 to 18 carbon atoms.

[0015] By amphoteric surfactant, we can cite, as non-limiting examples, betaine, imidazoline derivatives, alkyl amide carboxylate, sodium lauriminodipropionate.

[0016] Within the scope of the invention, compounds of the semi-developed formula CH 3 OC 3 H 6 OC 3 H 6 OH include dipropylene glycol methyl ether of formula CH 3 O[CH 2 CH(CH 3 )O] 2 H and any isomer.

[0017] It is clear from the above, and in particular from the range of sectors in which pesticide products are used and the quantities involved, that it is essential to develop effective, low-concentration and harmless active ingredients.

[0018] The invention provides a solution with a pesticidal or repellent active ingredient consisting of a combination of an unsaturated terpene compound chosen from geraniol, citronellal and a mixture of geraniol and citronellal, at least one anionic surfactant and / or a non-ionic surfactant and at least one solvent chosen from a compound of the semi-developed formula (I) CH 3 OC 3 H 6 OC 3 H 6 OH, ethyl lactate and a mixture of said compound (I) and ethyl lactate. In the above definition, the expression "at least one" means "one or more". Given the constituents involved in this active ingredient and the low levels necessary to obtain pesticidal or repellent effectiveness, this active ingredient perfectly meets the current need.It was further observed, unexpectedly, that a combination of the constituents according to the above invention made it possible to achieve insecticidal performances that combinations of the prior art based on geraniol or citronellal could not achieve even by increasing the geraniol or citronellal content, a ceiling of the insecticidal values being observed.

[0019] Advantageously, the surfactant is anionic. As will be illustrated in the examples, the anionic surfactant may be chosen from a secondary alkane sulfonate(s) and a lauryl sulfate, and mixtures thereof. The lauryl sulfate is, for example, chosen from sodium lauryl sulfate, ammonium lauryl sulfate, magnesium lauryl sulfate.

[0020] According to a preferred embodiment of the invention, the solvent is dipropylene glycol methyl ether of formula CH 3 O[CH 2 CH(CH 3 )O] 2 H.

[0021] In a pesticide or repellent active ingredient of the invention, the content of terpene compound(s) is preferably 0.5-30% by mass relative to the mass of the active ingredient, that of anionic and / or non-ionic surfactant(s) is 5-60% by mass relative to the mass of the active ingredient, the remainder being provided by the aforementioned solvent(s), i.e. a content of 10-94.5% by mass relative to the mass of the active ingredient. Within the above ranges of values, the contents of terpene compound(s) and of anionic and / or non-ionic surfactant(s) are essentially selected with a view to obtaining a manipulable active ingredient, i.e. having a sufficiently homogeneous presentation and a viscosity which allows it to be easily withdrawn, for example to obtain diluted formulations.

[0022] The invention also relates to a pesticide or repellent composition which comprises an active ingredient of the invention, a diluent and / or additives. The active ingredient may be present in a content ranging from 0.5 to 90% by mass relative to the mass of the composition. This composition may be in the form of a concentrate containing at least one active ingredient of the invention, a diluent, or even additives. In this format of the invention, it advantageously comprises 20-90% by mass of said active ingredient. It is then intended to be diluted in water, an alcohol such as ethanol or isopropanol, or a hydroalcoholic mixture, water being preferred, however. An advantageous dilution in that it leads to an effective pesticide or repellent composition which is of little or no harm, comprises 0.5-15% by mass of active ingredient relative to the mass of the diluted composition, and better still 0.5-5%.

[0023] As indicated above, a composition of the invention may comprise additives, these are chosen to be compatible with the constituents of the active ingredient on the one hand, and the uses for which the composition is intended on the other hand. They are conventional and well known to those skilled in the art. By way of examples, they may be inert additives making it possible to transport the pesticide or repellent active ingredient, additives making it possible to potentiate the synergistic action of the constituents of the active ingredient, additives making it possible to improve the appearance of the composition, to perfume it, or to reinforce its interest by a complementary action.

[0024] Among these additives, some are preferred; they can be used alone or in combination; they are as follows: essential oils other than geraniol and citronellal, such as peppermint essential oil; one or more sugars, in particular monosaccharides such as glucose and fructose; salts, in particular chlorides and sulfates of sodium, magnesium, calcium, potassium; these may be provided, at least in part, by seawater which is the diluent and they are present in the form of chloride, sulfate, sodium, magnesium, calcium and potassium ions.

[0025] According to a preferred implementation of the invention, a ready-to-use pesticide or repellent composition comprises 0.5-5% by mass of an active ingredient of the invention, 10-98% by mass of fructose, and optionally the balance of water, preferably sea water, or the balance of water and ethanol.

[0026] The invention also relates to any non-therapeutic use of a combination of an unsaturated terpene compound chosen from geraniol and citronellal or a mixture of geraniol and citronellal, at least one anionic and / or non-ionic surfactant and at least one solvent chosen from a compound of the semi-developed formula (I) CH 3 OC 3 H 6 OC 3 H 6 OH, ethyl lactate and a mixture of said compound (I) and ethyl lactate, as a pesticidal or repellent active ingredient. According to the invention, this use extends to any composition comprising a aforementioned active ingredient and a diluent as described above, and optionally any suitable additive, and preferably after dilution in an aqueous, alcoholic or hydroalcoholic solvent.

[0027] The present invention is now illustrated by the following examples highlighting, through comparative tests, the advantages of the invention, and in particular its insecticidal performance.

[0028] The preparation of the tested compositions and the insecticide tests to which they are subjected are described below.

[0029] The geraniol and citronellal used are commercially available and are of synthetic origin.

[0030] The anionic surfactants illustrated below are: the paraffin sulfonate (designated by SAS) used is identified under CAS no. 97489-15-1, it is a sulfonate of secondary alkane (C14-C17) and sodium, sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES), sodium lauryl sarcosinate (sarkosyl), and sodium stearate.

[0031] The nonionic surfactants illustrated below are: deceth 8 and polyethylene glycol trimethylnonylether (TMN) (as marketed under the name TERGITOL ®< 15S7).

[0032] The percentages of surfactants mentioned in Table 1 below are understood to be 100% (m / m) of dry extract.

[0033] The propylene glycol monomethyl ether (designated DPM) tested according to the invention is commercially available.

[0034] The various combinations based on geraniol or citronellal tested are prepared by simple mixing of the constituents at room temperature, some are supplemented with peppermint essential oil and each resulting combination is diluted in water and ethanol to obtain a composition of active ingredient. As a control, aqueous compositions of geraniol, geraniol and peppermint essential oil (EO), citronellal, and citronellal and peppermint essential oil (EO) are tested.

[0035] The compositions of the invention thus prepared are presented in the following Table 1, which indicates the percentage by mass of each constituent relative to the mass of the final composition.

[0036] The compositions in Table 1 are diluted in water at concentrations varying from 0.5% to 30% by mass before evaluation, to obtain each of them according to the target, a concentration by weight of geraniol or citronellal (%G / C) as determined in Table 2 below.

[0037] The insecticidal efficacy of the compositions thus obtained against all insects or multi-insect efficacy is evaluated on the following targets: the German cockroach (Blattella germanica) as a representative of crawling insects, including ants, fleas, ticks, earwigs, lice, the mosquito (of the species Aedes Aegypti, responsible for dengue fever in particular) as a representative of flying insects, the bedbug (of the species Cimex Lectularius, a parasite of humans and particularly widespread), the moth (Tineola bisselliella), known as the clothes moth, belonging to the family Tineidae, the ant (Lasius niger), the black garden ant which is a cosmopolitan species of ant of the subfamily Formicinae, the oriental cockroach, Blatta orientalis, which is a cosmopolitan species of cockroach and the second most common species found in homes, the fly, Musca domestica, the most common species of fly, and the tick, Ixodes Ricinus,on the rise for several decades in many regions of the northern hemisphere, it plays an important, even major, ecoepidemiological role in the transmission of certain diseases (Lyme disease for example).

[0038] The test followed is an adaptation of the ASTM E 654-96 standard for cockroach sprays. It is based on the document Technical Notes for Guidance on Product Evaluation, Product Type 18 and Product Type 19 (CA December 2012).

[0039] The insects are placed on a 14 cm diameter filter paper in a glass cylinder. A direct spray of 2 g of each composition contained in a disposable laboratory sprayer is applied to the insects from a distance of 30 cm. A control test in which the insects are not treated is carried out in parallel.

[0040] An insect is considered dead when it does not move normally.

[0041] The result of the insecticide evaluation against German cockroaches and bedbugs is expressed by the shortest duration chosen from the following values: 5 min, 15 min, 30 min, 1 h, 2 h, 24 h, 48 h and 72 h for which a 100% insect mortality rate is observed. The results are considered poor if a 100% mortality rate is not obtained within 72 h.

[0042] The results of the insecticide evaluation against mosquitoes, moths and ants are considered poor if a 100% mortality rate is not achieved within 5 minutes.

[0043] The multi-insect properties of a composition are confirmed when it is effective against both the German cockroach, the mosquito and the bedbug.

[0044] The results of these tests on German cockroaches, mosquitoes, moths, bedbugs and ants are presented in Table 2 below and the results of these tests on Oriental cockroaches, flies and ticks are presented in Table 3 below. The compositions of the invention tested comprise an active ingredient of the invention based on geraniol or citronellal, an anionic surfactant or a non-ionic surfactant, and a solvent chosen from dipropylene glycol methyl ether (DPM) or ethyl lactate (LE) and optionally additives such as peppermint essential oil (MP) and fructose and a diluent chosen from water, ethanol and a mixture of water and ethanol.

[0045] The first column of Tables 2 and 3 mentions the formulation of the composition outside the invention or the reference of the composition according to the invention mentioned in Table 1, and the other columns indicate the time necessary for a composition in a content expressed as a percentage by mass relative to the composition, or a control, to kill 100% of the insects. Table 2 Composition Target %G / C German cockroaches %G / C Mosquitoes %GC Moths %G / C Bedbugs %G / C Ants Geraniol 2 24 hours 0,5 5 min 0,5 5 min 2 24h 2 24h Citronellal 2 >7 days 0,5 5 min 0,5 5 min 2 >7 days 2 >7 days Geraniol 90% + MP 10% 2* 24h 0,5 5 min 0,5 5 min 2 24h 2 24h Citronellal 80% + MP 20% 2** >7 days 0,5 5 min 0,5 5 min 2 24h 2 >7 days 1 0,5 5 min 0,5 5 min 2 2h 2 2h 2 2 5 min 0,5 5 min 0,5 5 min 2 5 min 2 5 min 3 0,5 5 min 0,5 5 min 2 4h 2 2h 4 2 30 min 0,5 5 min 0,5 5 min 2 15 min 2 5 min 5 2 5 min 0,5 5 min 0,5 5 min 2 5 min 2 5 min 6 2 30 min 0,5 5 min 0,5 5 min 2 5 min 2 5 min 9 2 2h NT NT NT NT 10 2 4h NT NT NT NT 11 2 2h NT NT NT NT 12 2 30 min NT NT NT NT 13 2 4h NT NT NT NT 14 2 4h NT NT NT NT 15 2 4h NT NT NT NT * %G+MP ** %C+MP NT not tested

[0046] All the compositions of the invention display an insecticidal power much higher than that of geraniol or citronellal against targets that are very difficult to eradicate, such as German cockroaches or bedbugs. The most effective formulas are compositions 2, 4, 5, 6 and 12 of the invention, whose insecticidal power against German cockroaches and bedbugs (except for composition 12, which was not tested) is greatly increased compared to compositions of the prior art. Furthermore, a dazzling effectiveness is clearly improved compared to geraniol or citronellal alone. Table 3 Composition Target %G / C Oriental cockroaches %G / C Flies %G / C Ticks Geraniol 2 7 days NT NT Citronellal 3 >7 days NT NT Citronellal 80% + MP 20% 2* >7 days NT NT 2 2 5 min 1 5 min 2 15 min 4 3 48h 3 5 min NT 5 2 1h 2 5 min NT 6 3 48h 3 5 min NT 7 2 2h 0,5 5 min NT 8 2 2h 0,5 5 min NT *%C+MP NT not tested

[0047] Table 3 shows that the compositions according to the invention confirm their effectiveness, and in particular formula 2 which shows exceptional effectiveness against the oriental cockroach with a result of 100% insect mortality in just 5 minutes. These results also clearly broaden the spectrum of activity on other types of insects.

[0048] These results explicitly demonstrate the performance of the objects of the invention.

Claims

1. A pesticidal or repellent active ingredient consisting of a combination of an unsaturated terpene compound selected from among geraniol, citronellal and a mixture of geraniol and citronellal, at least one anionic surfactant and / or one nonionic surfactant, and a solvent selected from among a compound of semi-structural formula (I) CH3OC3H6OC3H6OH, ethyl lactate and a mixture of said compound (I) and ethyl lactate.

2. The pesticidal or repellent active ingredient according to claim 1, characterized in that the anionic surfactant is selected from among a secondary alkane sulfonate and a lauryl sulfate, as well as mixtures thereof.

3. The pesticidal or repellent active ingredient according to claim 1 or 2, characterized in that said compound (I) is dipropylene glycol methyl ether of formula CH3O[CH2CH(CH3)O]2H.

4. The pesticidal or repellent active ingredient according to any one of claims 1 to 3, characterized in that it consists of 0.5-30 weight% of the terpene compound(s), 5-60 weight% of the anionic and / or nonionic surfactant(s) and 10-94.5 weight% of the solvent(s).

5. A pesticidal or repellent composition characterized in that it comprises an active ingredient according to any one of claims 1 to 4, a diluent and / or additives.

6. The pesticidal or repellent composition according to claim 5, characterized in that it comprises 0.5-90 weight% of said active ingredient.

7. The pesticidal or repellent composition according to claim 5 or 6, characterized in that it comprises at least one additive selected from among a peppermint essential oil, a sugar and salts.

8. The pesticidal or repellent composition according to claim 7, characterized in that the sugar is selected from among glucose and fructose.

9. The pesticidal or repellent composition according to any one of claims 5 to 8, characterized in that the salts are selected from among chlorides and sulfates of sodium, magnesium, calcium and potassium.

10. The pesticidal or repellent composition according to any one of claims 5 to 9, characterized in that the diluent is seawater and in that the salts are, at least in part, supplied by the seawater.

11. The pesticidal or repellent composition according to any one of claims 5 to 10, characterized in that it comprises 0.5-5 weight% of said active ingredient, 10-98 weight% of fructose, and possibly the balance being water, preferably sea water, or the balance being water and ethanol.

12. A non-therapeutic use of a combination of an unsaturated terpene compound selected from among geraniol and citronellal or a mixture of geraniol and citronellal, at least one anionic surfactant and / or one nonionic surfactant, and at least one solvent selected from among a compound of semi-structural formula (I) CH3OC3H6OC3H6OH, ethyl lactate and a mixture of said compound (I) and ethyl lactate, as a pesticidal or repellent active ingredient.

13. The non-therapeutic use according to claim 12, characterized in that the active ingredient is diluted in water, an alcohol or a hydroalcoholic mixture.