VOC COMPOSITION AND ITS MINERAL SUPPORT

Abstract

VOC COMPOSITION AND MINERAL SUPPORT The present invention relates to a composition of volatile organic compounds (VOCs) that are either insect repellent or attractive, comprising a mixture of VOCs and a mineral carrier. The invention relates to the use of this VOC composition in agriculture, particularly in fields, to protect plants from damage caused by insect pests.

Description

Title of the invention: VOC COMPOSITION AND ITS MINERAL SUPPORT FIELD OF THE INVENTION

[0001] The present invention relates to a composition of volatile organic compounds (VOCs) having an effect on the behavior of insects (repellent or attractive), which comprises a mixture of VOCs and a mineral carrier. The invention relates to the use of the VOC composition in agriculture, in particular in fields to protect plants against damage caused by insect pests. STATE OF THE ART

[0002] Protecting crops against insect pests essentially involves the use of insecticide molecules which have the advantage of effectively eliminating pests, but the disadvantage of also eliminating other insects, such as pollinators, and of forming residues which pollute the surrounding soil and water tables. This is particularly the case with neonicotinoids which act at low doses on the central nervous system of insects, both harmful and pollinators.

[0003] Legislation in various countries has led to a ban on the use of these insecticides, but it is important to be able to provide concrete and effective alternatives to insecticides to enable farmers to produce more sustainably.

[0004] The use of essential oils in biocontrol for agriculture is known. Essential oils of different origins have been described for their herbicidal (Alipour et al. 2019), fungicidal or bactericidal properties (Ydmaz et al., 2021; Ben-Jabeur et al. 2019; De Clerc C. et al., Foods, 2020, 9 (10), 1418) or even insecticidal (Mossa TH, J.; of Environmental Science and Technology, 2016, 9 (5), 354-378) including against nematodes (Nguyen, M.-H et al., Archives of Phyto-pathology and Plant Protection 2022, 55 (4), 420-432).

[0005] The ability of certain VOCs to attract or repel insects is known (WO 2006 / 040766), in particular through the use of essential oils, complex mixtures of VOCs (WO 1996 / 039827; Kowalska, J. et al., Molécules, 2021; Deletre et al., 2015; Obeng-Ofori et al., 1997; Araujo et al., 2012; Zhang et al., 2013) or certain mixtures which have repellent or attractive properties (WO 2016 / 077495; EP 3 031 322; EP 3 874 948; US 4,880,624, WO 2004028256; WO 2011 / 045596; WO 2014 / 147110; US 2016 / 0302411; WO 2022 / 034085; Thôming G, Knudsen GK, Phy-tochemistry. 2014;100:66-75; von Arx M et al., J Insect Physiol. 2011; 57(10):1323-31) or which induce defense mechanisms in plants susceptible to attack by insect pests (US 8,221,736). Their use to repel aphids is also described (Dardouri, Tarek, et al., Agricultural and Forest Entomology, 2019; Dardouri, Tarek, et al., Pest management science, 2019; Dardouri, Tarek, et al., IOBC-WPRS Bull, 2017; Hori, Masatoshi, Journal of Chemical Ecology, 1998).

[0006] However, although the repellent or attractive properties of VOC mixtures are proven, their use in fields on a large scale remains limited due to constraints specific to these VOC mixtures and their mode of action. In particular, there is currently no effective solution that allows easy application in fields, using known conventional agricultural techniques, and a sufficient duration of effectiveness to ensure crop protection over several days.

[0007] The aim is to have a formulation which meets several objectives allowing this use of VOCs in agriculture, and in particular: - a simple formulation to spread with a mechanized spreader; - the most “stable” diffusion kinetics and “lifespan” of the for longest possible mulation (i.e. 4 to 8 weeks, at least), with a VOC diffusion rate above the target level of effectiveness with a presence of all VOCs throughout the duration of the application; and - a “resilient” formulation to climatic hazards, in particular leaching, temperature variations and UV radiation

[0008] The object of the present invention is to propose an effective biocontrol solution for use in agriculture. Statement of the invention

[0009] The present invention relates to a volatile organic compound (VOC) composition which comprises a mixture of VOCs and a silicate-based mineral carrier.

[0010] The invention also relates to the use of the VOC composition in agriculture. DEFINITIONS

[0011] By "volatile organic compound" or "VOC" is meant organic compounds that evaporate at room temperature.

[0012] By “room temperature” we mean a temperature ranging from 15 to 40°C, more generally from 20 to 30°C.

[0013] By "VOC mixture" is meant a composition consisting of VOCs chosen from allelochemical substances, in particular kairomones and allomones. It may include negligible traces of non-volatile impurities. The VOC mixture consists of at least 99% VOCs, more generally 100% VOCs. The VOC mixture may be a natural extract, a plant essential oil, or a "synthetic" or "manufactured" mixture, meaning that it is not found as such in nature. It is obtained by mixing pure VOCs or those already in mixtures with other VOCs.

[0014] “Kairomones” are VOCs produced by an emitting living organism, which produce a favorable effect for another living organism called a receiver, when they are released into the environment.

[0015] “Allomones” are VOCs produced by individuals of a first so-called emitting species which induce in individuals of another so-called receiving species a reaction favorable to the emitting species.

[0016] By “repellent VOC mixture” is meant a mixture of VOCs of known composition, selected for its repellent properties with respect to an insect, in particular an aerial insect.

[0017] By “attractive VOC mixture” is meant a mixture of VOCs of known composition, selected for its attractive properties towards an insect, in particular an aerial insect.

[0018] By "natural VOC mixture" is meant a mixture of VOCs obtained by extraction from a living organism, in particular a plant. Natural VOC mixtures are essentially made up of essential oils.

[0019] By "mixture of synthetic VOCs" or also called "manufactured", we mean a mixture of VOCs of predetermined composition obtained by mixing pure VOCs or already in mixtures with other VOCs.

[0020] By “support” is meant a material allowing the preservation of the VOC mixture, in particular during storage of the composition, its dosage and its use. The support is inert with respect to the VOC mixture.

[0021] By "support suitable for its use in agriculture" is meant a support which is furthermore suitable for the application of the repellent or attractive composition according to methods usual in agriculture and the release of VOCs after application.

[0022] By "use in agriculture" or "use in agriculture" is meant the application of the VOC composition in fields near cultivated plants, on the plants or at the base of the plants. By "in the fields" is meant both in a field in the open air and in a greenhouse. These are growing conditions in an uncontrolled atmosphere (in a field) or a poorly controlled atmosphere (in a greenhouse), with only certain temperature and / or humidity parameters generally being controlled.

[0023] Unless otherwise indicated, percentages are by weight.

[0024] An indication of numeric ranges by the endpoints is intended to include all the numbers included in this range (for example, a recitation of 1 to 5 includes, among others, 1, 1.25, 1.5, 1.75, 2, 2.45, 2.75, 3, 3.80, 4, 4.32, 4.45 and 5).

[0025] The term "about" is used here explicitly or implicitly. Each given quantity in this description refers to the given actual value, and to the approximation to that given value that would be reasonably inferred based on ordinary skill in the art, including equivalents and approximations due to experimentation and / or measurement conditions for that given value. In general, the term "about" in the context of a given value or range refers to a value or range that is within 5% of the given value or range, especially less than 1%. DESCRIPTION OF FIGURES

[0026] [Fig.l] represents the results of a study of the diffusion of VOCs from granules according to the invention in the field in an uncontrolled atmosphere on a first site (Site 1) located in Eure, in Normandy. The diffusion rate is given for all the VOCs in the mixture.

[0027] [Fig. 2] represents the results of a study of the diffusion of VOCs from granules according to the invention in the field in an uncontrolled atmosphere on a second site (Site 2) located in Loiret, in the Loire Valley. The diffusion rate is given for all the VOCs in the mixture.

[0028] [Fig.3] represents the results of analysis and individual measurement of diffusion of the 3 VOCs of the mixture on the 2 sites (site 1 located in Eure, in Normandy and site 2 located in Loiret, in Val de Loire); VOC1: linalool, VOC 2: eugenol and VOC3: trans-cinnamaldehyde. DETAILED DESCRIPTION Mineral Support

[0029] The support is suitable for its use in agriculture, that is to say it allows the application of the repellent or attractive composition in fields near cultivated plants, or at the foot of the plants according to usual agronomic methods.

[0030] The support is inert with respect to the VOC mixture, that is to say that it does not produce reactions with the VOCs of the mixture in a substantial manner such that the mixture would be modified during the preservation and storage of the composition.

[0031] The support is a silica-based mineral support. Among the silica-based mineral supports, mention will be made in particular of diatomaceous earth, precipitated silica, clays, lithothamnium, kaolinite and zeolites and their mixtures.

[0032] According to a preferred embodiment, the silica-based mineral support is diatomaceous earth. Diatomaceous earth, also called diatomite, celite or kieselguhr, is a siliceous sedimentary rock of organic and fossil origin, consisting of fossilized remains of diatoms.

[0033] The silica-based mineral support, and in particular diatomaceous earth, is in a powder form with a particle size generally between 1 and 200 pm. Advantageously, the mineral support has a D50 distribution of at least 5 pm, preferably at least 6 pm, more preferably at least 7 pm.

[0034] Preferably, the silica-based mineral support and in particular diatomaceous earth has a specific surface area of ​​at least 20 m2 / g, in particular at least 25 m2 / g, at least 30 m2 / g. In particular, the specific surface area of ​​the mineral support ranges from 20 to 60 m2 / g, more particularly from 25 to 55 m2 / g, preferably from 30 to 50 m2 / g, in particular from 30 to 45 m2 / g.

[0035] According to a particular embodiment, the mineral support comprises at least about 70% by weight of diatomaceous earth, more particularly at least about 80%, about 90%, at least about 95%. According to a more particular embodiment, the mineral support is essentially made up of diatomaceous earth. Silica-based mineral supports and in particular diatomaceous earth are commercially available, in particular marketed under the name DIAMOL® by the company IMERYS and also manufactured by companies such as Atlantic Equipment Engineers, Inc., Twin Specialties, Noah Chemicals, Barentz, EP Container Corp., BariteWorld etc. Different producers of diatomaceous earth are notably referenced on the site https: / / www.thomasnet.com / products / diatomaceous-earth-25193400-l.html. Mixture of VOCs

[0036] Any mixture of VOCs having attractive or repellent properties towards insects can be used in the VOC composition according to the invention. The VOC mixtures can be natural or synthetic.

[0037] VOCs, their formulas, their effects on different insects and references to the articles which describe them can be found in particular on the site https: / / www.pherobase.com, in particular kairomones (https: / / www.pherobase.com / database / compound / compounds-behav-kaines.php), allomones (https: / / www.pherobase.com / database / compound / compounds-behav-allnes.php), and those identified as repellents (https: / / www.pherobase.com / database / compound / compounds-behav-repnts.php).

[0038] Mixtures of VOCs and their repellent or attractive action on various aerial insects are described in particular in patent applications EP 0 629 345, US 2016 / 0255833, WO 2021 / 155257 and WO 2021 / 041927 and in the references cited above.

[0039] According to a first embodiment, the mixture of VOCs is a mixture of natural VOCs.

[0040] Among the mixtures of natural repellent VOCs, we will mention the essential oils of rue (Ruta graveolens), thyme (Thymus vulgaris), lemongrass (Cymbopogon citratus) cumin (Cuminum cyminum), lavender (Lavandula x Intermedia), verbena (Verbena officinalis ), geranium (Pelargonium sp), mint, especially spearmint (Mentha spicata) and peppermint (Mentha x piperita), eucalyptus, especially lemon eucalyptus (Corymbia citriodora) and eucalyptus globulus, cedar (Cedrus libani), clove (Syzygium aromaticum), rosemary (Rosmarinus officinalis), garlic (Allium sativum), celery (Apium graveolens), juniper (Juniperus communis), nepetas (Nepeta spp), oregano (Origanum vulgare), cymbopogon (Cymbopogon citratus), pepper piper spp), cinnamon (Cinnamomum spp), Chinese cinnamon (Cinnamomum cassia), caraway (Carum carvi), dracocephalum moldavicum, fennel (Foeniculum vulgare), Hyssop (Hyssopus officinalis), lemon balm (Melissa officinalis), basil (Ocimum basilicum), sage (Salvia spp), coriander (Coriandrum sativum), clove (Syzygium aromaticum), neem (Azadirachta indica), marigolds (Tagetes patula) and dill (Anethum graveolens). Essential oils can be used alone or in blends.

[0041] According to a particular method, to repel flea beetles, in particular for rapeseed, we will cite an essential oil chosen from the essential oils of Ruta graveolens, Thymus vulgaris, Cymbopogon citratus, Cuminum cyminum, Lavandula, Verbena of-ficinalis, Pelargonium sp, Mentha spicata, Mentha x piperita, Corymbia citriodora, Cedrus libani, Syzygium aromaticum, Rosmarinus officinalis, eucalyptus globulus, used alone or in mixtures.

[0042] According to another particular method, the essential oils of Rosmarinus officinalis, Allium sativum, Apium graveolens, Juniperus virgina, Mentha spicata, Nepeta Cataria, Litsea cubeta, Satureja montana, Thymus vulgaris, Thymus serpyllum, Origanum compactum, Cymbopogon schoenanthus, Piper nigrum, Cinnamorum verum, Cinnamomom cassia and Origanum majorata, used alone or in mixtures, will be mentioned for repelling thrips, in particular for tomatoes.

[0043] According to another particular method, the essential oils of Carum carvi, Citrus sinensis (L.) Osbeck, Dracocephalum kotschyi, Eucalyptus globulus Labill., Foeniculum vulgare Mill, Hyssopus officinalis, Lavandula angustifolia, Melissa officinalis L, Mentha piperita, Mentha pulegium Mill., Ocimum basilicum L, Majorana hortensis L., Origanum vulgare, Pimpinella anisum, Thymus capitatus, Verbena officinalis L, Hemizygia petiolata, Melissa officinalis, Salvia officinalis, Coriandrum sativum, Cinnamomum verum, Syzygium aromaticum, Azadirachta indica, Tagetes erecta, Allium sativum and Ruta graveolens, used alone or in mixtures, will be mentioned to repel aphids, in particular for beets and peppers.

[0044] According to yet another method, the essential oils of Cinnamomum cassia, Mentha x piperita, Pimpinella anisum, Ocimum basilicum, Mentha spicata, Anethum graveolens, used alone or in mixtures, will be cited to repel the green pea aphid.

[0045] A person skilled in the art will be able to select as a mixture of VOCs having an effect on the behavior of insects used for according to the invention the essential oil in relation to the targeted aerial insect pest, in particular according to the plant / aerial insect pest combinations described above.

[0046] According to a second embodiment of the invention, the VOC mixture is a synthetic VOC mixture.

[0047] While it is possible to consider the use of a single VOC as a "VOC mixture", the literature teaches a better effectiveness of mixtures which include at least two different VOCs. Advantageously, the synthetic mixture includes from 2 to 5 different VOCs, 2, 3, 4 or 5 different VOCs whose proportions will vary depending on the targeted insect.

[0048] The VOCs used in the synthetic mixture may be of natural origin, extracted from plants in particular, or synthetic. Whether they are of natural or synthetic origin, the VOCs used in the mixture according to the invention have a purity of at least 95%, advantageously at least 96%, at least 97%, at least 98%, at least 99%.

[0049] Mention will be made in particular of eugenol, linalool, cinnamaldehyde, in particular transcinnamaldehyde, geraniol, caryophyllene, para-cymene, gamma-terpinene, alpha-terpinene, alpha-phellandrene, epizingiberene, nerolidol, famesol, geraniol, anisaldehyde, coumarin, methyl jasmonate, cis-jasmone, salicylaldehyde, alpha-pinede, eucalyptol, citral monoterpenoid, (E)-2-hexenal, and carvacrol. In particular, the synthetic VOC mixture comprises at least one VOC chosen from eugenol, linalool, cinnamaldehyde.

[0050] According to a particular embodiment of the invention, the mixture of synthetic VOCs is a mixture that repels aphids.

[0051] Among the aphids, pests of crops of these plants, we will mention the aphids of the genera Acyrthosiphon (Acyrthosiphon pisum, Acyrthosiphon malvae), Aphis (Aphis lambersi, Aphis spiraecola, Aphis fabae, Aphis gossypii, Aphis nastutii, Aphis craccivora, Aphis forbesi, Aphis frangulae), Aulacorthum (Aulacorthum solani, Aulacorthum circumflexum), Brachycaudus (Brachycaudus helichrysi), Brevicoryne (Brevicoryne brassicae), Cavariella (Cavariella aegopodii), Chaetosiphon (Chaetosiphon (Pentatrichopus) fragaefolii), Diuraphis (Diuraphis spp). Dysaphis (Dysaphis apifolia, Dysaphis crataegi, Dysaphis plant agineap Hyadaphis (Hyadaphis foeniculi, Hyadaphis passerini), Lypaphis (Lipaphis erysimi), Macrosiphum (Macrosiphum eu-phorbiae), Megoura (Megoura viciae), Metopolophium (Metopolophium dirhodum, Metopolophium festucae), Myzus (Myzus persicae, Myzus ascalonicus, Myzus ornatus), Nazonovia (Nazonovia ribisnigrii), Neactaphis (Nearctaphis bakeri).Neotoxptera ( Neotoxoptera formosana, Neotoxoptera oliveri), Rhodobium ( Rhodobium porosum), Rhopalosiphoninus ( Rhopalosiphoninus staphyleae, Rhopalosiphum padi, Rhopa- . losiphum insertum, Rhopalosiphum maidis, Rhopalosiphoninus latysiphon), Schizaphis (Schizaphis graminum), Semiaphis (Semiaphis dauci), Sipha (Sipha (Rungsia) elegans, Sipha (Rungsia) maydis), Sitobion (Sitobion avenue, Sitobion fragariae), Smyn-thurodes (Smynthurodes betae), Trama (Trama spp) and Therioaphis (Therioaphis trifolii )•

[0052] Aphids are known to affect a wide variety of crops, including Apiaceae (Umbelliferae), such as carrots, celery or root or aromatic plants such as parsley, fennel, angelica, cumin; Asteraceae, including oilseeds such as sunflower, an oilseed plant or market garden plants such as lettuce, chicory, endive, artichoke, salsify, salsify, or aromatic, medicinal or ornamental plants such as asters or chrysanthemums; Brassicaceae (Cruciferae), including oilseeds such as rapeseed, or vegetable brassicaceae; Chenopodiaceae such as beets, spinach, chard or cardoon; Cucurbitaceae, such as melons, squash, zucchini, cucumbers, gherkins, pumpkins, watermelons;Fabaceae (legumes), of large crops such as clover, sainfoin, alfalfa, pea, protein pea, field bean or lupin, or of market garden crops such as beans, peas, lentils or broad beans; Liliaceae (Aliaceae), such as leek, onion, shallot, garlic or asparagus; Poaceae, including straw cereals, wheat, barley, oats or rye, forage grasses, cocksfoot, fescue, timothy or ryegrass or corn; Solanaceae such as potatoes, tomatoes, eggplant and pepper.

[0053] The aphid-repellent synthetic VOC mixture comprises at least linalool and eugenol. It preferably comprises less linalool than eugenol.

[0054] According to one embodiment, the linalool / eugenol weight ratio ranges from about 1 / 4 to about 2 / 3, and in particular about 2 / 7, about 1 / 3, about 3 / 8, about 2 / 5, about 3 / 7, about 4 / 9, about 1 / 2, about 5 / 9 and about 3 / 5. In particular, the linalool / eugenol weight ratio is between any one of these fractions, in particular between about 2 / 7 and about 1 / 2, between about 1 / 3 and about 5 / 9, between about 3 / 8 and about 3 / 5. According to a particular embodiment, the linalool / eugenol weight ratio is at least about 1 / 3, in particular at least about 3 / 8, more particularly at least about 2 / 5. According to another particular embodiment, the linalool / eugenol weight ratio is less than about 1 / 2, in particular less than about 4 / 9. According to another particular embodiment, the linalool / eugenol weight ratio ranges from about 3 / 8 to about 4 / 9. Advantageously, the linalool / eugenol weight ratio is about 2 / 5 or about 3 / 7.

[0055] According to a particular embodiment, the VOC mixture comprises at least linalool, eugenol and cinnamaldehyde, in particular trans-cinnamaldehyde. The content of trans-cinnamaldehyde in the VOC mixture is less than or equal to the content of linalool + eugenol mixture, preferably lower.

[0056] According to one embodiment, the weight ratio trans-cinna-maldehyde / (linalool+eugenol) ranges from about 2 / 7 to about 1 / 1, and in particular about 1 / 3, about 3 / 8, about 2 / 5, about 3 / 7, about 4 / 9, about 1 / 2, about 5 / 9, about 3 / 5 and about 2 / 3. In particular, the weight ratio trans-cinna-maldehyde / (linalool+eugenol) is between any one of these fractions, in particular between about 1 / 3 and about 3 / 5, between about 3 / 8 and about 5 / 9, between about 2 / 5 and about 1 / 2. According to a particular embodiment, the weight ratio trans-cinnamaldehyde / (linalool+eugenol) is at least about 1 / 3, in particular at least about 3 / 8, more particularly at least about 2 / 5. According to another particular embodiment, the weight ratio trans-cinnamaldehyde / (linalool+eugenol) is less than approximately 5 / 9, in particular less than approximately 1 / 2, even more particularly less than approximately 4 / 9.According to another particular embodiment, the weight ratio trans-cinnamaldehyde / (linalool+eugenol) ranges from approximately 2 / 5 to approximately 1 / 2. Advantageously, the weight ratio trans-cinnamaldehyde / (linalool+eugenol) is approximately 3 / 7.

[0057] In this definition, the quantity of linalool and eugenol in the linalool+eugenol+trans-cinnamaldehyde mixture is preferably according to a linalool / eugenol weight ratio as defined above.

[0058] The mixture of synthetic VOCs may comprise other VOCs chosen from kairomones and allomones. In particular, geraniol and caryophyllene will be mentioned.

[0059] According to a particular embodiment, the content of linalool and eugenol (linalool + eugenol) is at least 30% by weight of the total weight of the VOC mixture, more particularly at least 35%, 40%, 45% or 50% by weight. According to a more particular embodiment, the content of linalool and eugenol is at least 60% by weight of the total weight of the VOC mixture, more particularly at least 65% to 100%.

[0060] According to one embodiment, the VOC mixture comprises a. 5 to 40% of linalool, in particular 15 to 35%, b. 25 to 80% of eugenol, in particular 40 to 75%, and c. 0 to 50% of trans-cinnamaldehyde, in particular 10 to 40%,

[0061] the total a+b+c being less than or equal to 100% and the relative contents of each constituent being defined above.

[0062] According to a particular embodiment of the invention, the VOC mixture comprises a. 15 to 25% of linalool, in particular approximately 20%, b. 45 to 55% eugenol, especially about 50%, and c. 25 to 35% trans-cinnamaldehyde, especially about 30%,

[0063] the total a+b+c being equal to 100%.

[0064] According to a more particular embodiment, the VOC mixture comprises linalool, eugenol and trans-cinnamaldehyde in a weight ratio of 2 / 5 / 3.

[0065] When the total a+b+c is less than 100%, the mixture comprises other VOCs, more particularly other kairomones or allomones described above in relative quantities whose addition to a+b+c equals 100%.

[0066] Mention will in particular be made of a composition comprising a. 5 to 20% linalool, b. 25 to 40% eugenol, c. 30 to 45% trans-cinnamaldehyde, d. 5 to 15% geraniol, and e. 5 to 15% caryophyllene,

[0067] the total a+b+c+d+e being equal to 100%. VOC composition

[0068] The silica-based mineral support, particularly diatomaceous earth, is porous and the VOC mixture is absorbed into the mineral support.

[0069] According to one embodiment, the weight ratio of VOC mixture / mineral support is at least 1 / 5, in particular at least 1 / 4, at least 2 / 7, at least 2 / 5, at least 1 / 2, at least 3 / 5, up to 3 / 4 or more.

[0070] According to one embodiment, the mineral support is saturated with a VOC mixture. The VOC mixture / mineral support weight ratio will depend on the support used and its specific surface area. For diatomaceous earth, the VOC mixture / diatomaceous earth weight ratio is at least 3 / 5, in particular from 3 / 5 to 3 / 4, in particular approximately 2 / 3.

[0071] The VOC composition is in solid form, in particular in powder or granule form.

[0072] The powders advantageously have a particle size of 1 to 1000 μm.

[0073] The granules advantageously have a particle size of 2 to 10 mm, in particular of 2.5 to 6 mm, including 3, 3.5, 4, 4.5, 5, 5.5 mm. The particle size is measured using standard techniques for measuring granule size on sieves.

[0074] The VOC mixture being adsorbed on the mineral support, the size of the granules essentially corresponds to the size of the mineral support granules.

[0075] The composition may comprise binder compounds or coatings usual for the formulation of powders or granules, such as cellulose derivatives, talc, starch, molasses, dextrins, gelatin, waxes, mineral waxes or vegetable waxes, gums, polymers or oils (vegetable, mineral, synthetic, natural, etc.). It may also comprise other additives usual for the preparation of powders or granules, such as colorants, preservatives, anti-foaming agents, anti-caking agents.

[0076] According to one embodiment, the VOC content in the composition is at least 10% by weight relative to the total weight of the composition, in particular at least 11, 12, 13, 14, 15 or 16% by weight. The content of VOC mixture will generally range from 10 to 35% by weight, relative to the total weight of the composition, in particular from 15 to 30% by weight. According to a preferred embodiment of the invention with diatomaceous earth as a mineral carrier, the composition comprises from 16 to 25% by weight of VOC mixture.

[0077] According to a particular embodiment, the composition is in the form of granules with a core consisting of the mineral support and a mixture of VOCs as defined above and a coating. The coating is carried out with any usual coating means / material used in agriculture. It is chosen so that it does not constitute a barrier to the diffusion of VOCs, in particular that the coating is neutral with respect to the diffusion of each VOC, that is to say that the diffusion takes place without modifying the relative proportions of each VOC of the diffused mixture. The coating means is in particular chosen from vegetable waxes, more particularly rapeseed wax.

[0078] According to a particular embodiment, the composition is in the form of granules, with diatomaceous earth as mineral support, a mixture of VOCs as defined previously and a coating of rapeseed wax.

[0079] The preparation of the VOC compositions according to the invention is carried out according to the usual methods for preparing powders and granules, coated or not.

[0080] The preparation comprises in particular the steps of: 1. impregnation of the mineral support with the VOC mixture, in particular by spraying the support with the VOC mixture and / or immersing the support in the VOC mixture, 2. optionally film coating and / or coating of the impregnated mineral support, and 3. optionally drying of the impregnated mineral support, where appropriate film coated and / or coated.

[0081] In particular for compositions in the form of granules, the method comprises obtaining the mineral support in the form of granules. The mineral support is generally initially in the form of powder, which must be granulated according to standard techniques by mixing the powder with a binder until the desired particle size is obtained. It is also possible to obtain granules, in particular diatomaceous earth granules.

[0082] Advantageously, the preparation of the composition in the form of granules comprises at least one coating step after impregnation with the VOC mixture.

[0083] The coating material, in particular vegetable wax, more particularly rapeseed wax, is melted and sprayed onto the impregnated carrier granules, or the impregnated carrier granules are immersed in the molten material. The coating may be achieved by repeating the spraying or immersion several times.

[0084] The preparation process may comprise a drying step, in particular after film-coating the granules. Use in Agriculture

[0085] The VOC composition according to the invention is particularly suitable for use in agriculture, in particular for repelling insect pests, keeping them away from the plants that one seeks to protect and in the vicinity or on which the VOC composition has been applied.

[0086] The invention therefore relates to the use in agriculture of a VOC composition according to the invention, to protect plants against damage caused by insect pests.

[0087] The plants are in particular cultivated plants, such as field crops or market garden plants. Among the plants used in agriculture, mention will be made of field crops and market garden plants, in particular the Apiaceae (Umbelliferae), such as carrots, celery or root or aromatic plants such as parsley, fennel, angelica, cumin; the Asteraceae, including oilseeds such as sunflower, an oilseed plant or market garden plants such as lettuce, chicory, endive, artichoke, salsify, scorzonera, or aromatic, medicinal or ornamental plants such as asters, or chrysanthemums; the Brassicaceae (Cruciferae), including oilseeds such as rapeseed, or vegetable brassicaceae; Chenopodiaceae such as beets, spinach, chard or chard; Cucurbitaceae, such as melons, squash, zucchini, cucumbers, gherkins, pumpkins, watermelons;Fabaceae (legumes), for field crops such as soybeans, clover, sainfoin, alfalfa, peas, protein peas, field beans or lupins, or for market garden crops such as beans, peas, lentils or broad beans; Liliaceae (Aliaceae), such as leeks, onions, shallots, garlic or asparagus; Poaceae, including straw cereals, wheat, barley, oats or rye, forage grasses, cocksfoot, fescue, timothy or ryegrass or corn; Solanaceae such as potatoes, tomatoes, eggplant and peppers.

[0088] Among the large-scale or industrial crops, we will mention in particular corn, wheat, barley, rapeseed, beetroot and peas. Among the market garden plants, we will mention in particular carrots, lettuce, leeks, peppers and tomatoes.

[0089] By "protecting plants against damage caused by insect pests" we mean protecting the aerial parts of cultivated plants against the activities of insect pests (feeding, egg-laying). These attacks can cause defoliation, necrosis, growth retardation, disease transfer (viruses, fungi) on plants, and ultimately a reduction in the quality of the harvest.

[0090] When the VOC mixture is a repellent mixture, the composition according to the invention will be identified as a repellent composition and will be applied near the plants to be protected, or on these plants.

[0091] By "proximity to the plant" we generally mean a distance between the area of ​​application of the repellent composition and the stem of the plant which will depend in particular on the surface of the soil covered by the leaves at the development stage of the application. It ranges in particular from 0 (on contact) to approximately 80 cm.

[0092] Advantageously, each plant will be near an appropriate amount of VOC composition.

[0093] The invention therefore also relates to a method for protecting plants against damage caused by insect pests, said method consisting of applying to the plant and / or to the soil near the plant, an appropriate quantity of repellent composition according to the invention.

[0094] The application is carried out according to the usual methods used in agriculture for spreading powders or granules.

[0095] It can be made alone, or combined with other products for improving and / or controlling pests and other diseases of cultivated plants. Advantageously, the application of the repellent composition according to the invention makes it possible to limit, and preferably to avoid, the use of insecticides.

[0096] The appropriate amount of repellent composition is generally between 100 g / ha and 3 kg / ha depending on the composition used.

[0097] The composition according to the invention is applied as needed for prevention of the time when insects are likely to appear or for treatment after the appearance of insects on the plants.

[0098] According to a particular method suitable for the protection of cultivated plants, the composition having an effect on insect behavior (repellent, attractive, etc.) is applied in preventive mode from the emergence of the seedlings (cotyledon stage). Depending on the pressure exerted by insects during the growth of the plants, the application of the repellent composition may be repeated at least once.

[0099] When the VOC mixture is an attractive mixture, the composition according to the invention will be identified as an attractive composition and will be applied at a distance from the plants to be protected, so as to keep away the insect pests to be protected.

[0100] According to a particular method, the attractive composition will be applied to a cultivation plot separate from the plants to be protected.

[0101] By cultivation plot distinct from the plants to be protected, we mean a predetermined area of ​​the field, or greenhouse, where the plants are cultivated, the surface area of ​​which represents less than 10% of the total cultivated surface, advantageously less than 5% of the total cultivated surface. The cultivated plants are all treated with the composition attractive. These plants are said to be "sacrificed" to keep insect pests away from the cultivated plants to be protected.

[0102] This predetermined area may be unique or divided into several sub-units distributed around or within the cultivated plants to be protected.

[0103] According to a particular method, this predetermined area is located around the cultivated plants to be protected.

[0104] According to another particular mode, the predetermined area is located within the cultivated plants to be protected.

[0105] According to another particular mode, the predetermined area is located around and within the cultivated plants to be protected.

[0106] A person skilled in the art will be able to determine the predetermined area, its location and its surface area based on parameters specific to the crop in question and parameters specific to the cultivated area, and in particular its geographical configuration.

[0107] According to a particular embodiment of the invention, the composition is a repellent composition and the plants are sugar beets.

[0108] Diatomaceous earth is known for various uses in agriculture related to its absorbent properties, which cause the desiccation of gastropods, and / or abrasive properties, which cause the death of crawling insects upon contact with it. The protective effect demonstrated for the present invention is independent of any contact of the insect pests with the support comprising the diatomaceous earth. The protective effect is due to the mixture of VOCs in the composition, whether it is a repellent or attractive mixture, to keep insect pests away from the plants to be protected. EXAMPLES

[0109] The present invention will be better understood by reading the following examples which illustrate the invention in a non-limiting manner. Materials and methods

[0110] Preparation of formulations of a mixture of VOCs with a silica-based mineral support

[0111] VOC mixture: linalool / eugenol / trans-cinnamaldehyde in a weight ratio of 2 / 5 / 3

[0112] Mineral support: Diatomaceous earth granules with a particle size of 3 to 6 mm.

[0113] Coating: rapeseed wax

[0114] The VOC composition is prepared by immersing the diatomaceous earth granules in the VOC mixture, and then the impregnated diatomaceous earth granules are coated with rapeseed wax by dipping in molten rapeseed wax at 65°C.

[0115] The “core” of the granules consists of diatomaceous earth granules impregnated with the VOC mixture represents 80% of the total mass of a granule. This percentage is given as an average value measured for a set of several granules.

[0116] Granules were prepared for VOC / Carrier weight ratios of 40 / 60, 50 / 50 and 60 / 40. Diffusion tests showed optimal diffusion for the 40 / 60 ratio.

[0117] The following tests are carried out with granules comprising approximately 48% diatomaceous earth, approximately 32% VOC mixture and approximately 20% rapeseed wax coating. Example 1 - Spreading Granules

[0118] The spreading of granules is mainly done with a self-propelled spreader of the anti-slug spreader type also called a seed spreader. Other spreading methods, by drone, by autonomous robot are also possible.

[0119] The spreader can be attached to a quad bike, a tractor or any other compatible motorized equipment. The granules are usually spread in a contiguous band. The width between two spreader passes is generally between 20 and 30m. The spreader spreads the granules by projection over a width of between 10 and 15m on each side. The spreading dose in kg / ha is adjusted according to a ratio of forward speed in km / h and the opening diameter of the flow hatch in mm. Some equipment allows the rotation speed of the disc that projects the granules to be adjusted, which allows the spreading width to be adjusted.

[0120] The characteristics of the granules allow the most homogeneous spreading possible for a dose of between 3 and 10 kg / ha. The particle size of the granules is between 3 and 6 mm in diameter, with a centered distribution between 3.5-4.5 mm in diameter. One kg of granules contains between 30,000 and 50,000 grains so as to allow homogeneous spreading over a width of 20 to 30 m. Example 2 - Monitoring VOC diffusion in fields

[0121] Field diffusion tests under uncontrolled atmospheric conditions were carried out at two sites with different climates in terms of humidity, sunshine and winds. The first site (Site 1) ([Fig.l]) is located in Eure, Normandy, and the second site (Site 2) ([Fig.2]) is located in Loiret in the Loire Valley.

[0122] Aging process in external conditions

[0123] In order to describe the behavior of the granules and quantify the diffusion levels, granule samples were aged and analyzed every week for 4 weeks. Several samples with a mass of 0.357g of granules corresponding to the dose equivalent to 1 m2 of spreading were aged in the field, on different sites. The climatic conditions (T°, rainfall, enso (lighting) were measured in order to correlate them with the diffusion results. Each week, 3 replicates of granule samples were analyzed for diffusion in the laboratory in order to measure the diffusion rate.

[0124] The diffusion of VOCs from the granules was studied using the dynamic headspace technique. The granules recovered from the field are analyzed in the laboratory according to the protocol described below. The granules are enclosed in a closed chamber (headspace) and an air flow is circulated which then passes through an absorbent cartridge (VOC Trap, Vassays) using a pump (Gilair Plus) and a flow meter to control the air flow (900 ml / min) for 30 minutes. The adsorbed VOCs are eluted in a vial using pure hexane (200 μl). The liquid samples are then analyzed by gas chromatography coupled with mass spectrometry (Scion SQ GC-MS 436). The result is shown in the form of a curve or histogram on which the evolution over time of the diffusion rates (expressed in %) is displayed, i.e. the concentrations of VOCs in the air of the headspace.

[0125] Chemical analyses (see [Fig.3]) show that the three VOCs of interest are present for 28 days. The granules allow for stable diffusion of VOCs over time.

[0126] For good field effectiveness, it is desired to have at least a 10% diffusion rate, preferably in a range of 10% to 40% diffusion rate. It should be noted that a diffusion rate greater than 40% does not affect the effectiveness of the composition.

[0127] The results shown in Figures 1 and 2 show that under different climatic conditions, the diffusion rate is maintained above 10% for at least 15 days, up to almost 30 days at the northernmost Site 1.

[0128] It can be seen from this test that a new application 15 days after the first ensures at least a 10% diffusion rate at the location where the granules are spread.

[0129] The results shown in [Fig.3] show that at both sites, the 3 VOCs of the mixture remain present throughout the duration of the test.

Claims

Claims

1. Composition of volatile organic compounds (VOCs), characterized in that it comprises a mixture of VOCs and a silica-based support.

2. Composition according to claim 1, characterized in that the silica-based mineral support is chosen from diatomaceous earth, precipitated silica, clays, lithothamne, kaolinite and zeolites and their mixtures.

3. Composition according to claim 2, characterized in that the silica-based mineral support is diatomaceous earth.

4. Composition according to one of claims 1 to 3, characterized in that the mineral support is in a powder form with a particle size generally between 1 and 200 μm.

5. Composition according to one of claims 1 to 5, characterized in that the mineral support has a D50 distribution of at least 5 pm, preferably at least 6 pm, more preferably at least 7 pm.

6. Composition according to one of claims 1 to 5, characterized in that the silica-based mineral support has a specific surface area of ​​at least 20 m2 / g, in particular at least 25 m2 / g, at least 30 m2 / g.

7. Composition according to one of claims 1 to 6, characterized in that the mixture of VOCs is a natural mixture, in particular chosen from essential oils of rue (Ruta graveolens), thyme (Thymus vulgaris), lemongrass (Cymbopogon citratus) cumin (Cuminum cyminum), lavandin (Lavandula x Intermedia), verbena (Verbena officinalis), geranium (Pelargonium sp), mint, in particular spearmint (Mentha spicata) and peppermint (Mentha x piperita), eucalyptus, in particular lemon eucalyptus (Corymbia citriodora) and eucalyptus globulus, cedar (Cedrus libani), clove (Syzygium aromaticum), rosemary (Rosmarinus officinalis), garlic (Allium sativum), celery (Apium graveolens), juniper (Juniperus communis), nepetas (Nepeta spp), oregano (Origanum vulgare), cymbopogon (Cymbopogon citratus), pepper piper spp), cinnamon (Cinnamomum spp), Chinese cinnamon (Cinnamomum cassia), caraway (Carum carvi), dracocephalum moldavicum), fennel (Foeniculum vulgare),hyssop (Hyssopus officinalis), lemon balm (Melissa officinalis), basil (Ocimum basilicum), sage (Salvia spp), coriander (Coriandrum sativum), clove (Syzygium aromaticum), neem (Azadirachta indica), marigolds (Tagetes patula) and dill (Anethum graveolens and mixtures thereof.,

8. Composition according to one of claims 1 to 6, characterized in that the mixture of VOCs is a synthetic mixture.

9. Composition according to claim 8, characterized in that the synthetic mixture comprises at least one VOC chosen from eugenol, linalool, cinnamaldehyde, in particular trans-cinnamaldehyde, geraniol, caryophyllene, para-cymene, gamma-terpinene, alpha-terpinene, alpha-phellandrene, epizingiberene, nerolidol, famesol, geraniol, anisaldehyde, coumarin, methyl jasmonate, cis-jasmone, salicylaldehyde, alpha-pinene, eucalyptol, citral monoterpenoid, (E)-2-hexenal, and carvacrol, in particular at least one VOC chosen from eugenol, linalool and cinnamaldehyde.

10. Composition according to one of claims 1 to 9, characterized in that the weight ratio of VOC mixture / mineral support is at least 1 / 5, in particular at least 1 / 4, at least 2 / 7, at least 2 / 5, at least 1 / 2, at least 3 / 5.

11. Composition according to one of claims 1 to 10, characterized in that it is in the form of powder or granules.

12. Composition according to claim 11, characterized in that it is in the form of granules with a particle size of 2 to 10 mm.

13. Composition according to claim 12, characterized in that the granules are coated with a vegetable wax, in particular a rapeseed wax.

14. Composition according to one of claims 1 to 13, characterized in that the VOC content in the composition is at least 10% by weight relative to the total weight of the composition, in particular 10 to 35% by weight, more particularly 15 to 30%.

15. Use in agriculture of a VOC composition according to one of claims 1 to 14, to protect plants against damage caused by insect pests.

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