WO2024208945A1 - Improved waxy delivery forms for oily agronomic active ingredients and method of preparation - Google Patents

Improved waxy delivery forms for oily agronomic active ingredients and method of preparation Download PDF

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Publication number
WO2024208945A1
WO2024208945A1 PCT/EP2024/059138 EP2024059138W WO2024208945A1 WO 2024208945 A1 WO2024208945 A1 WO 2024208945A1 EP 2024059138 W EP2024059138 W EP 2024059138W WO 2024208945 A1 WO2024208945 A1 WO 2024208945A1
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WO
WIPO (PCT)
Prior art keywords
oil
wax
inhibitors
agronomic
oily
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PCT/EP2024/059138
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French (fr)
Inventor
Davide DE SIMEIS
Giorgio Freschi
Emma MAZZEI
Stefano ZUCCHINALI
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Clever Bioscience S.R.L.
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Publication of WO2024208945A1 publication Critical patent/WO2024208945A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/20—Fabaceae or Leguminosae [Pea or Legume family], e.g. pea, lentil, soybean, clover, acacia, honey locust, derris or millettia
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides

Definitions

  • the invention relates to the field of products used in agronomy such as insecticides, fungicides, antimicrobials, herbicides and similar, and to methods to increase their efficacy.
  • Pesticides and biocides are usually administered by spraying or by topic uses (biocides).
  • their use has a negative effect in the environment (spray of pesticides) both in the short term as well as in the long term, by increasing the environmental pollution or, when the biocides are used in contact with the skin (repellents body solution), by increasing the possible negative dermal effects represented by sensitization and allergy.
  • the pesticides and biocides active substance can be incapsulated.
  • EP 183, 999 describes microcapsules containing pyrethrum extract (an insecticide) obtained by using synthetic polymers such as polyurea, polyesters, polyamides and so on;
  • US 10,271,547 B2 describes microcapsules composed of lipidic-waxy cores containing pheromone and encapsulated in copolymers of (meth) acrylic acids and alkyl acrylates supplemented with hydrophobic macromonomers; the microcapsules are suspended in an aqueous medium for administration.
  • Further microcapsules prepared in a similar way and containing insecticides are described also in GB 2, 187,957, EP322,820 and EP 902,724, in Gimeno M., J. Environ. Sci.
  • microplastic is typically considered to refer to small, usually microscopic, solid particles made of a synthetic polymer. They are associated with long-term persistence in the environment, if released, as they are very resistant to (bio) degradation and are practically impossible to remove from the environment after release.
  • ECHA European Chemicals Agency
  • W02007/063267 relates to compositions comprising terpenes and hollow glucan particles or cell wall particles and methods for preparing such compositions.
  • the compositions increase terpene stability and activity and provide a suitable carrier for the terpenes.
  • the invention also relates to methods of using such compositions in the medical, veterinary and agricultural fields.
  • WO2016/ 124927 describes a composition comprising a microparticle component and a highly potent active agent encapsulated in the microparticle.
  • WO2010/ 101821 describes various microencapsulated insecticide formulations for the control of pests such as aphids and beet army worm.
  • WO 2006/077568 refers to a novel 'green' agricultural formulation comprising at least one encapsulated volatile essential oil and a non-volatile vehicle in which said at least one encapsulated volatile essential oil is carried.
  • EP815144 is related to a novel composition composed of a gelling agent and glucan and its use as a nutritional supplement, cosmetic product, etc. as a medical device as a pharmaceutical incorporated into the medical device.
  • WO2018/201161 discloses platforms, compositions and methods for encapsulating agricultural compounds in achromosomal and/or anucleated cells.
  • US5009898 relates to antimicrobial hydroxyapatite powders, wherein metal ions having an antimicrobial property such as silver, copper and zinc ions, or organic antimicrobial agents such as hinokitiol, tannin, lysozyme, protamine and sorbic acid are included in hydroxyapatite powders having good affinity for a living body.
  • WO20 17/ 134308 describes a process for the production of lignin nanoparticles comprising a hydrophobic active agent.
  • US 2021/0244034 describes a solid composition, comprising a volatile active composition, e.g.
  • CN 1156694 describes a highly fluid antifungal coating composition containing beeswax, citronella oil and olive oil.
  • Granular pesticidal compositions are known from US 5,827,540 and US 2006/0099233: these document describe granules massively made of inorganic carrier; the active agent is applied externally as a coating, in a mixture with minor amounts of a waxy substance.
  • US 2003/0108584 discloses a premixed powder for agronomic use including highly disperse silica, minor amounts of wax and even minor amounts of oil.
  • Aqueous emulsions whose lipophilic component include waxy substances and oils are known, for application in technical fields different from agronomy: cf. eg. the publication Cellulose, 2020, 17, pp.9711-9723 (used for impregnation of textiles), US 6,358,623 (used for the treatment of domestic surfaces like furniture, floors, etc.), CN 106479381 (used as shoe polish); none of these products is meant for preparation of granules and/or includes inorganic carriers.
  • the Applicant is actively engaged in the field of pesticides/ biocides delivery via natural carrier products, aiming to products which are safe for the worker and for the environment, overcome relevant technical and environmental limits, and can be released efficiently into the environment over extended periods of time.
  • Aim of the present invention is to find novel pesticide products, based on the use of natural or synthetic pesticides, using biodegradable polymers, providing an efficient long-lasting effect.
  • a further aim is to make available improved intermediate products suitable for the preparation of a variety of pesticide products having the above characteristics.
  • compositions wherein oily agronomic active ingredients are mixed with waxes and inorganic carriers within specific weight ranges.
  • the compositions include an oily agronomic active ingredient and a wax in a weight ratio comprised between 1.20: 1 and 2.80: 1; they also include an inorganic carrier in a weight ratio between 1.70: 1 and 2.40: 1 with respect to the sum of oily agronomic active ingredient and wax. All these ingredients are uniformly dispersed in the composition.
  • the compositions are optimally suited for being further processed into granules which, after administration to an agronomic surface such as soil or plants are characterized by a sustained duration of action and resistance to leaching by environmental factors.
  • oily agronomic active ingredient and the wax are mixed a lipophilic solvent and a surfactant within specific weight ranges to obtain oily dispersions suitable for administration to an agronomic surface such as soil or plants, characterized by a sustained duration of action an excellent resistance to leaching by environmental factors.
  • compositions are entirely homogeneous in their structure, and are used to prepare correspondingly homogeneous products, in particular granules or oily dispersions, with reproducible levels of activity and resistance to environmental leaching after application onto agronomic surfaces.
  • All the compositions and products object of the invention are water-free; in addition, due to their homogeneous structure, they are different from multiphasic or multi-structured products, e.g. coated cores, etc., which are accordingly not part of the invention. Accordingly, throughout this application, the terms “mix”, “mixed”, “mixing”, “mixtures” indicate the formation of homogeneous systems. Also the term “matrix” used herein indicates a homogeneous mixture of its components.
  • the invention is herein defined by various ranges, defined by a lower and upper limit and the expression, “between/ and” or “from/to”, equivalent and used indifferently for the purpose of the invention. Said upper and lower limits, all values between them, sub-ranges, and combinations thereof are part of the invention.
  • ily agronomic active ingredient indicates a lipophilic fluid product which is immiscible with aqueous solvents (for reference, distilled water at 20° C) and is freely miscible with organic solvents (for reference: methylene chloride at 20°C), having a kinematic viscosity of up to 100 mm 2 /sec at 20°C and ambient pressure, measured in standard conditions, cf. Eur. Pharmacopoeia 10.0 (2.2.9 Capillary viscosimeter method).
  • agronomic active ingredient defines any agronomic active ingredient which is “oily” as above defined; however, the term also extends to agronomic active ingredients which are not oily but are dissolved or dispersed in carrier oils; the carrier oils are "oily” as defined above, and remain such after dissolution therein of the agronomic active ingredient.
  • the weight of the “oily agronomic active ingredient” is meant as a whole, thus also including the carrier oil, when present.
  • carrier oils are vegetable oils like e.g. rape seed oil, sunflower oil, soy oil, olive oil and the like, modified vegetable oils e.g. alkoxylated sun flower or soy oil, or synthetic oils. More generally, carrier oils can be chosen within the following classes of compounds, provided that they are “oily” as defined above: (tri)glycerides like e.g. technical mixtures of mono, di and triglycerides of C6-C22 fatty acids, fatty acid alkyl esters e.g.
  • esters of vegetable oils fatty acid alkyl esters based on said C6-C22 fatty acids, etc.
  • esters of linear C6-C22-fatty acids with branched alcohols in particular 2- ethylhexanol
  • esters of C18-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols linear or branched C6-C22- fatty alcohols, in particular dioctyl malates
  • esters of linear and/or branched fatty acids with polyhydric alcohols such as e.g.
  • the wax used in the invention can be conveniently selected from currently available waxes. According to their origin, the waxes are divided into three groups, i.e. natural, chemically modified or synthetic waxes; preferred are the natural or chemically modified waxes; most preferred are natural waxes.
  • Natural waxes include plant waxes (e.g. candelilla wax, carnauba wax, japan wax, espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, etc.), animal waxes (e.g., beeswax, shellac wax, spermaceti, lanolin or wool wax, uropygial grease, etc.), and mineral waxes (e.g., ceresin, ozokerite or earth wax, etc.); particularly preferred are myrtle wax, rice wax, candelilla wax, mimosa wax, carnauba wax, soy wax, beeswax.
  • plant waxes e.g. candelilla wax, carnauba wax, japan wax, espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, etc.
  • waxes including hard waxes (e.g., montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, etc.);
  • hard waxes e.g., montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, etc.
  • synthetic waxes including polyalkylene waxes, polyalkylene glycol waxes (e.g., polyethylene glycol waxes), etc.
  • esters of a long-chain alcohol (preferably C12 to C32) with a fatty acid (preferably C12 to C32) which are solid a room temperature can be regarded as waxes.
  • the weight ratio oily agronomic active ingredient to wax is comprised between 1.20: 1 and 2.80: 1; preferably it is comprised between 1.25: 1 and 2.70: 1; most preferably, it is comprised between 1.30: 1 and 2.65: 1.
  • the waxy substance which is mainly responsible for adherence of the composition to the substrate to which it is applied, has the further advantage of being selectable from fully natural or nature- derived product, advantageously replacing any synthetic substances used in the prior art for the same purpose.
  • lipophilic matrix The oily agronomically active ingredient and the wax, considered as a whole, are herein indicated as “lipophilic matrix”: the attribute “lipophilic” derives from the presence of the wax and the oily agronomic active ingredient, both having lipophilic character; the term “matrix” highlights a structural function for the co-presence of these ingredients within the composition.
  • the above compositions further contain an inorganic carrier, which contributes to their structural performance.
  • the inorganic carrier can be chosen from currently available ones. Examples thereof are: silica type materials such as sand, broken walnut hulls, argillaceous materials such as clay of the montmorillonite, kaolinite or other types, diatomaceous earths, zeolite, chabazite, clinoptilolite, leonardite, andalusite, ball clay, bentonite, calcium aluminate, feldspar, fused alumina, halloysite, mica, moler, mullite, zirconia, wallostonite, chamotte, perlite, carbon black, and other low density materials such as granulated corn cobs and other organic derivatives; talc, quartz, graphite, and many other inert materials with a variety of densities and other useful, relatively insoluble cores include agricultural minerals such as sulfur, gypsum, lime.
  • the weight ratio of inorganic carrier to lipophilic matrix is comprised between 1.70: 1 and 2.40: 1. In more preferred embodiments it is comprised between 1.75: 1 and 2.35: 1; in most preferred embodiments, it is comprised between 1.80: 1 and 2.30: 1.
  • the inorganic carrier has preferably an average particle size between 30 and 85 gm.
  • the combination of the ratio lipophilic ingredient:wax (from 1.20: 1 to 2.80: 1) with the ratio inorganic carrier: lipophilic matrix (from 1.70: 1 to 2.40: 1) obtains a rather fluid lipophilic matrix which is then mixed with a moderate excess of solid carrier, obtaining a “soft product” endowed with sustained release properties and good adhesivity properties once in contact with the plant or soil.
  • any agronomic active ingredient can be used in the present invention. If they are “oily” as defined by the present application, they can be used as such; if not, they can be dissolved or suspended in a carrier oil, forming therewith the oily agronomic active ingredient in accordance with the invention.
  • the oily agronomic active ingredient is one or more essential oils, used alone or, optionally, dissolved or dispersed in carrier oils.
  • essential oils are: aromatic plant extracts selected from the group consisting of extracts of Abies sibirica, Malpighia glabra, Achillea millefolium.
  • said aromatic plant extract is selected from the group consisting of extracts of Mentha piperita, Mentha Spicata, Thymus vulgaris, Salvia officinalis, Rosmarinus officinalis, Sesamus indicum, Syzygium aromaticum, Allium sativum, Citrus lemon, Cinnamomum verum, Origanum vulgaris, separately or in mixture.
  • Particularly preferred essential oils are: clove oil, neem oil, cinnamon oil, cedar oil, castor oil, geranium oil, lemongrass oil, mint oil, thyme oil, turmeric oil, Wintergreen oil, rosemary oil , anise oil, cardamom oil, chamomile oil coriander oil, cumin oil, dill oil, mint oil, parsley oil, lavender oil, basil oil, camphor oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil, grapefruit oil, lemon oil, mandarin oil, orange oil, pine needle oil, pepper oil, rose oil, sweet orange oil, tangerine oil, tea tree oil, tea seed oil, caraway oil, garlic oil, peppermint oil, onion oil, spearmint oil, terpenes, azadiractin, spynosyns, sesquiterpenes, oxygenated sesquiterpenes, phenyl propanoids.
  • the agronomic active ingredient can be independently selected, for example, in one or more of the following classes of insecticides, fungicides, antimicrobials, nematicides, herbicides, semiochemicals. Mixtures of agronomic active ingredients belonging to the same class and/or to different classes can also be used.
  • the insecticides can be selected e.g. in the classes of: Acetylcholine esterase (AchE) inhibitors; Sodium channel modulators; Nicotinic acetylcholine receptor (nAChR) agonists; Nicotinic acetylcholine receptor allosteric activators; Chloride channel activators; Juvenile hormone mimics; Chordotonal organ TRPV channel modulators; Mite growth inhibitors; Microbial insecticidal proteins; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nicotinic acetylcholine receptor (nAChR) channel blockers; Inhibitors of chitin biosynthesis; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; electron transport inhibitors of Mitochondrial complex I, II or III; Voltage-dependent sodium channel blockers; Inhibitors of acetyl CoA carboxylase; Ryanodine receptormodulators
  • Preferred insecticides are selected among pyrethroids and among and neonicotinoids, such as Bifenthrin, Deltamethrin, Permethrin, Sumithrin, Tetramethrin, Transfluthrin, acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam.
  • neonicotinoids such as Bifenthrin, Deltamethrin, Permethrin, Sumithrin, Tetramethrin, Transfluthrin, acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam.
  • the fungicides can be selected e.g. in the classes of: Respiration inhibitors; Sterol biosynthesis inhibitors; Nucleic acid synthesis inhibitors; Inhibitors of cell division and cytoskeleton; Inhibitors of aminoacid and protein synthesis; Signal transduction inhibitors; Protein inhibitors; Inhibitors with Multi Site Action; Cell wall synthesis inhibitors; Plant defences inducers.
  • Preferred fungicides are chosen among azoxystrobin, boscalid, carboxin, fenfuram, azaconazole cyproconazole , prothioconazole, difenoconazole, diniconazole, diniconazole-epoxiconazole, fenbuconazole, tebuconazole, imazalil, prochloraz, triflumizol, fenarimol, pyrifenox, triforine, valifenalate.
  • antimicrobials can be selected e.g. in the class of antimicrobial peptides.
  • Antimicrobial peptides are a class of small peptides that widely exist in nature and they are an important part of the innate immune system of different organisms and have a wide range of inhibitory effects against bacteria, fungi, parasites and viruses
  • Suitable antimicrobial peptides are described in Norine platform (see Norine: update of the nonribosomal peptide resource.
  • the antimicrobial peptides are beauvericins; cyclic depsipeptides, aureobasidins, cyclosporins.
  • nematicides are chemical agents used to control parasitic worms such as roundworms and threadworms. In one preferred embodiment, they are selected from Oxamyl, Fluensulfone, Fluopyram, Ethoprop. In another preferred embodiment nematicides are clove oil, eugenol.
  • the herbicides can be selected e.g. in the classes of: lipid biosynthesis inhibitors; acetolactate synthase inhibitors; photosynthesis inhibitors; protoporphyrinogen-IX oxidase inhibitors; bleacher herbicides; enolpyruvyl shikimate 3 -phosphate synthase inhibitors (EPSP inhibitors); glutamine synthetase inhibitors; 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); mitosis inhibitors; inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); cellulose biosynthesis inhibitors; decoupler herbicides; auxinic herbicides; auxin transport inhibitors.
  • lipid biosynthesis inhibitors e.g. in the classes of: lipid biosynthesis inhibitors; acetolactate synthase inhibitors; photosynthesis inhibitors; protoporphyrinogen-IX oxidase inhibitors; bleacher herbicides; enolpyruvy
  • Preferred herbicides can be selected from protoporphyrinogen-IX oxidase inhibitors, enolpyruvyl shikimate 3 -phosphate synthase inhibitors, mitosis inhibitors and synthesis of very long chain fatty acids inhibitors (VLCFA inhibitors).
  • the semiochemicals can be selected e.g. in the classes of pheromones and kairomones. They can be selected from acyclic terpenes such as (Z,Z,Z)-3,6,9 triene C19-C21 hydrocarbon , (Z,Z)-6,9 diene C19-C21 hydrocarbon, their alcohols and esters, small ring terpenes such as limonene, sabinene, alpha terpineol, large ring terpenes such periplanone B,C,D,J , fused ring terpenes such as camphor, borneol, 3- carene, nepetaloctol, heterocyclic terpenes such asperillene, rose oxide.
  • acyclic terpenes such as (Z,Z,Z)-3,6,9 triene C19-C21 hydrocarbon , (Z,Z)-6,9 diene C19-C21 hydrocarbon
  • they are selected from L-carvone, citral, (E,Z)-7,9- dodecadien- l-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7, 11, 13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, methyl eugenol, methyl jasmonate, (E,Z)-2, 13-octadecadien- l-ol, (E,Z)-2, 13-octadecadien- l-ol acetate, (E,Z)-3, 13-octadecadien- l-ol, ⁇ -l-octen-3-ol, pentatermanone, (E,Z,Z)-3,
  • a further object of the invention is a process of producing the afore described compositions and granular products.
  • the process is generally characterized by the steps of:
  • step (bl) cooling the product of step (a) to a temperature below the melting point of the wax and mixing the resulting product with the inorganic carrier, or
  • step (b2) mixing the product of step (a) with the inorganic carrier and cooling the resulting product to a temperature below the melting point of the wax.
  • the resulting product can be further treated by conventional methods, for example by extrusion, to obtain a uniform granular formulation.
  • the weight ratio of oily agronomic active ingredient ingredient to wax is comprised between 1.20: 1 and 2.80: 1, and the weight ratio of inorganic carrier to lipophilic matrix [i.e. oily agronomic active ingredient + wax] is comprised between 1.70: 1 and 2.40: 1.
  • Preferred sub-ranges for these ratios in the present process those described above in relation to the composition.
  • All mixing steps are performed until a homogeneous mixture of all the components subjected to mixing is obtained.
  • the mixing is preferably performed by stirring.
  • step (a) the mixing is preferably performed at a temperature at least 10°C higher than the melting temperature of the wax.
  • the inorganic carrier has preferably an average particle size between 30 and 85 gm.
  • the mixing of the inorganic carrier with the lipophilic matrix can be conveniently performed at room temperature and in conventional mixers, obtaining a homogeneous mixture.
  • compositions as obtained or obtainable by the above- mentioned process, have typically a solid or semi-solid consistence; from this product, uniformly structured granules can be obtained by conventional means such as extrusion through a small sized mesh, e.g. with mesh size comprised between 1 and 3 mm, e.g. 2 mm.
  • the formed granular product is suitable for direct administration to the soil and/or plants, and does not require dissolution or dispersion in a water medium for subsequent irro ration.
  • the lipophilic and greasy character of the product assures a strong adherence to the soil or plant, opposing to water leaching, wind dispersion, protecting the active ingredient from degradation and assuring its sustained release over time.
  • a further object of the invention are the agronomic granular products obtained from the above-described composition. These products are characterized by a high specific activity (i.e. ratio between the found activity of the active ingredient and its administered amount), enhanced properties of sustained duration of action and good resistance to environmental agents, such as leaching by rainwater (rainfastness), wind, etc.
  • the granules are especially effective in high specific activity and sustained duration of action.
  • the invention also includes a method of applying, i.e. administering, the above-described granular agronomic formulation to a substrate.
  • Said applying is typically performed by dispersing the corresponding granular product in its own solid form, i.e. not vehicled by liquids.
  • the substrate of application is typically the soil or a plant or a plant parts in need thereof, with the advantage of the adhesivity of the product caused by its lipophilic and greasy character.
  • Plant parts to which to granular product is applicable can be selected, without limitation from: leaves, bark, fruits, flowers, seeds or roots of plants and crops; specific examples thereof are cereals beans peas, fruit trees walnut, chestnut, almond, leafy vegetables, fruiting vegetables, root crops, processing crops, cucurbitaceous plants, pasture plants, lawn grasses, perfumery crops, ornamental plants, timber woods, etc.
  • a composition wherein the oily agronomic active ingredient and the wax are homogeneously mixed in a mutual weight ratio comprised between 1.20: 1 and 3.80: 1 (preferably between 1.50: 1 and 3.60: 1; more preferably between 1.80: 1 and 3.40: 1) and are not associated with the inorganic carrier.
  • This composition also defined herein as “lipophilic matrix”, is further mixed with a lipophilic solvent and a surfactant, as additional ingredients.
  • the lipophilic solvent is added in a weight ratio to the oily agronomic active ingredient comprised between 1: 1 and 3: 1 (preferably between 1.2: 1 and 2.7: 1; more preferably between 1.3: 1 and 2.4: 1) and ii) the surfactant is added in a weight ratio to the oily agronomic active ingredient comprised between 0.20: 1 and 0.90: 1 (preferably between 0.24: 1 and 0.80: 1; more preferably between 0.28: 1 and 0.70: 1).
  • the resulting product (oily dispersion) is suitable for administration to an agronomic surface such as soil or plants, and is characterized by a sustained duration of action an excellent resistance to leaching by environmental factors.
  • the lipophilic solvent is additional to and different from the oily agronomical active ingredient and any components thereof: subject to this provision, the lipophilic solvent can be freely chosen with no criticality among any lipophilic solvents currently available. Accordingly, suitable lipophilic solvents can be chosen, without limiting the invention to one or more of the following:
  • esters of linear C6-C22-fatty acids with branched alcohols in particular 2 -ethylhexanol, esters of C18-C38-alkyl hydroxy carboxylic acids with linear or branched C6-C 22-fatty alcohols, in particular dioctyl malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol and/or Guerbet alcohols), triglycerides based on C6-C10-fatty acids, liquid mono-/ di-/ triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms
  • preferred solvents are, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13- carboxylic acids with linear or branched C6-C22-fatty alcohols, such as e.g., myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, ste
  • the other components of the composition according to the second main embodiment i.e. the oily agronomically active ingredient components (agronomically active ingredient and, when present, the oil) and the wax can be freely chosen within the same groups of compounds, among the same specific compounds, in the same grade of preferences and associability, as exemplified and claimed in relation to the first main embodiment.
  • the oily agronomically active ingredient components agronomically active ingredient and, when present, the oil
  • the wax can be freely chosen within the same groups of compounds, among the same specific compounds, in the same grade of preferences and associability, as exemplified and claimed in relation to the first main embodiment.
  • the second main embodiment can be described as a composition
  • a composition comprising, in homogeneous mixture: an oily agronomic active ingredient and a wax, having a weight ratio of oily agronomic active ingredient to wax comprised between 1.20: 1 and 3.80: 1 (preferably between 1.50: 1 and 3.60: 1; more preferably between 1.80: 1 and 3.40: 1), a lipophilic solvent and a wax.
  • the lipophilic solvent is present in a weight ratio to the oily agronomic active ingredient comprised between 1: 1 and 3: 1 (preferably between 1.2: 1 and 2.7: 1; more preferably between 1.3: 1 and 2.4: 1)
  • the surfactant is present in a weight ratio to the oily agronomic active ingredient comprised between 0.20: 1 and 0.90: 1 (preferably between 0.24: 1 and 0.80: 1; more preferably between 0.28: 1 and 0.70: 1).
  • Clove oil [oily agronomic active principle] have been heated at 50°C in presence of paraffin wax (1,5 kg). Once obtained a clear solution, the mixture was let to cool at room temperature and added to 8kg of bentonite under stirring in a professional mixer. The paste was then extruded in a pilot extruder using 2mm diameter mesh.
  • Example 2 Pyrethrum extract oily dispersion lkg of pyrethrum extract (50%) [oily agronomic active principle] is added to 2 kg of rapeseed oil [carrier oil]. The mixture has been heated at 50°C in presence of paraffin wax (1,5 kg). Once obtained a clear solution, the mixture was let to cool at room temperature. At this point, 4,5 kg of soybean methyl ester [lipophilic solvent] and 1 kg of the suitable alkyl sulfate surfactant have been added under agitation.
  • Aspochracin agronomically active principle
  • mandarin oil agronomically active principle
  • carvacrol agronomically active principle
  • the mixture has been heated at 70°C in presence of beeswax (100 mg). Once obtained a clear solution, the mixture was let to cool at room temperature. At this point, 390 mg of propylene-glycol methyl esters [lipophilic solvent] and 200 mg of the suitable non-ionic block-copolymeric surfactants have been added under agitation.
  • Example 6 nematicidal activity on tomato and cucumber (field trials)
  • Plots of 25m 2 of tomato seedlings have been set up to evaluate the efficacy of the formulated products described in example 1 and 4 against nematodes.
  • a commercial reference product against nematodes was used as control.
  • thermoplastic film section is allowed to dry at room temperature and the entire surface is then washed with 12mL of water using a standard spray system with 1mm nozzle.
  • the thermoplastic film section after washing is dried and then treated with ethanol 98%.
  • the collected solution is analyzed for the residual quantity of the products after washing by HPLC-MS
  • Plots of 5m 2 of tomato seedlings have been set up to evaluate residuality of the products described in example 2 and 3 on the leaf.
  • Table 6 The different products containing the respective active ingredient have been applied at a dosage of 2 L/ha by diluting the product in water sufficient to wet the culture well but limiting dripping (minimum 200 L/ha). After 4 hours the seedlings are sprinkled with water for 5 minutes to simulate a rain of 40 to 50 mm. The leaves have been let to dry. The leaves of each thesis, after drying, have been collected and analyzed to quantify the residual active ingredient.

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Abstract

New composition are provided, based on a combination of oily agronomic active ingredients with waxes within specific weight ratios. The compositions also include an inorganic carrier or, alternatively, a lipophilic solvent and a surfactant. All the ingredients are uniformly dispersed and the resulting compositions are optimally suited for being processed into granular products or oily dispersions characterized by a sustained duration of action and excellent resistance to leaching by environmental agents.

Description

Title: Improved waxy delivery forms for oily agronomic active ingredients and method of preparation
DESCRIPTION
FIELD OF THE INVENTION
The invention relates to the field of products used in agronomy such as insecticides, fungicides, antimicrobials, herbicides and similar, and to methods to increase their efficacy.
STATE OF THE ART
Pesticides and biocides are usually administered by spraying or by topic uses (biocides). However, their use has a negative effect in the environment (spray of pesticides) both in the short term as well as in the long term, by increasing the environmental pollution or, when the biocides are used in contact with the skin (repellents body solution), by increasing the possible negative dermal effects represented by sensitization and allergy. To dwindle these disadvantages, the pesticides and biocides active substance can be incapsulated.
Many encapsulation techniques are reported, in particular by using synthetic polymers to get a slow release of the actives contained in the capsules. So, formulations containing microcapsules having the most various characteristic and their related processes to get the microcapsules are known in the art. For example, Wege P.J. in Proceeding of the Third International Conference on Urban Pests describes microcapsules with polyurea wall containing lambda- cyhalothrin; Sheu E.Y. in 2000 BCPC Symposium Proceedings No.74 discloses the technology of the quick release microencapsulation of lambda-cyhalothrin based on the interfacial polymerization by using polymethylene-polyphenylisocyanate (PMPPI) and toluene diisocyanate (TDI) as crosslinking agent. EP 183, 999 describes microcapsules containing pyrethrum extract (an insecticide) obtained by using synthetic polymers such as polyurea, polyesters, polyamides and so on; US 10,271,547 B2 describes microcapsules composed of lipidic-waxy cores containing pheromone and encapsulated in copolymers of (meth) acrylic acids and alkyl acrylates supplemented with hydrophobic macromonomers; the microcapsules are suspended in an aqueous medium for administration. Further microcapsules prepared in a similar way and containing insecticides are described also in GB 2, 187,957, EP322,820 and EP 902,724, in Gimeno M., J. Environ. Sci. Health, 1996, B31 (3), 407-420, Finch C.A. “Encapsulation and controlled release”, Royal Society of Chemistry 1993, 138, 1- 12, in EP183999, WO 2003/051116, US2003/0119675, US2002/0158356 Al, WO 00/04776, EP 322820.
Nowadays, there are many concerns related to microplastics. The term ‘microplastic’ is typically considered to refer to small, usually microscopic, solid particles made of a synthetic polymer. They are associated with long-term persistence in the environment, if released, as they are very resistant to (bio) degradation and are practically impossible to remove from the environment after release.
As the most of the encapsulated products and related formulations into the agro-market are generally composed by synthetic polymers belonging to the above-mentioned chemical classes and the related pollution is playing a key point for the environment contamination, the European Chemicals Agency (ECHA) is preparing a restriction dossier on ‘microplastics” on the basis of Article 69(1) of the REACH Regulation.
For this reason, it is crucial to find new strategies to encapsulate pesticides and biocides through natural and biodegradable encapsulating materials. There are different approaches that can be pursued like microencapsulants based on polysaccharides, proteinbased microencapsulants, lipid/ liposome based microencapsulants, cell-based microencapsulants and mineral-based microencapsulants. For example, W02007/063267 relates to compositions comprising terpenes and hollow glucan particles or cell wall particles and methods for preparing such compositions. The compositions increase terpene stability and activity and provide a suitable carrier for the terpenes. The invention also relates to methods of using such compositions in the medical, veterinary and agricultural fields. WO2016/ 124927 describes a composition comprising a microparticle component and a highly potent active agent encapsulated in the microparticle. WO2010/ 101821 describes various microencapsulated insecticide formulations for the control of pests such as aphids and beet army worm. WO 2006/077568 refers to a novel 'green' agricultural formulation comprising at least one encapsulated volatile essential oil and a non-volatile vehicle in which said at least one encapsulated volatile essential oil is carried. EP815144 is related to a novel composition composed of a gelling agent and glucan and its use as a nutritional supplement, cosmetic product, etc. as a medical device as a pharmaceutical incorporated into the medical device. WO2018/201161 discloses platforms, compositions and methods for encapsulating agricultural compounds in achromosomal and/or anucleated cells. US5009898 relates to antimicrobial hydroxyapatite powders, wherein metal ions having an antimicrobial property such as silver, copper and zinc ions, or organic antimicrobial agents such as hinokitiol, tannin, lysozyme, protamine and sorbic acid are included in hydroxyapatite powders having good affinity for a living body. WO20 17/ 134308 describes a process for the production of lignin nanoparticles comprising a hydrophobic active agent. US 2021/0244034 describes a solid composition, comprising a volatile active composition, e.g. an essential oil, absorbed on a waxy sorbent; the waxy sorbent is prevalent, stated to represent 50% or more of the whole solid composition, while the active composition represents 50% or less: the examples describe wax-based compositions having an oikwax ratio of 0.6: 1. CN 1156694 describes a highly fluid antifungal coating composition containing beeswax, citronella oil and olive oil. Granular pesticidal compositions are known from US 5,827,540 and US 2006/0099233: these document describe granules massively made of inorganic carrier; the active agent is applied externally as a coating, in a mixture with minor amounts of a waxy substance. US 2003/0108584 discloses a premixed powder for agronomic use including highly disperse silica, minor amounts of wax and even minor amounts of oil.
Aqueous emulsions whose lipophilic component include waxy substances and oils are known, for application in technical fields different from agronomy: cf. eg. the publication Cellulose, 2020, 17, pp.9711-9723 (used for impregnation of textiles), US 6,358,623 (used for the treatment of domestic surfaces like furniture, floors, etc.), CN 106479381 (used as shoe polish); none of these products is meant for preparation of granules and/or includes inorganic carriers.
The Applicant is actively engaged in the field of pesticides/ biocides delivery via natural carrier products, aiming to products which are safe for the worker and for the environment, overcome relevant technical and environmental limits, and can be released efficiently into the environment over extended periods of time. Aim of the present invention is to find novel pesticide products, based on the use of natural or synthetic pesticides, using biodegradable polymers, providing an efficient long-lasting effect. A further aim is to make available improved intermediate products suitable for the preparation of a variety of pesticide products having the above characteristics.
SUMMARY
New compositions are provided, wherein oily agronomic active ingredients are mixed with waxes and inorganic carriers within specific weight ranges. The compositions include an oily agronomic active ingredient and a wax in a weight ratio comprised between 1.20: 1 and 2.80: 1; they also include an inorganic carrier in a weight ratio between 1.70: 1 and 2.40: 1 with respect to the sum of oily agronomic active ingredient and wax. All these ingredients are uniformly dispersed in the composition. The compositions are optimally suited for being further processed into granules which, after administration to an agronomic surface such as soil or plants are characterized by a sustained duration of action and resistance to leaching by environmental factors. Alternatively, the oily agronomic active ingredient and the wax are mixed a lipophilic solvent and a surfactant within specific weight ranges to obtain oily dispersions suitable for administration to an agronomic surface such as soil or plants, characterized by a sustained duration of action an excellent resistance to leaching by environmental factors. DETAILED DESCRIPTION OF THE INVENTION
The present compositions are entirely homogeneous in their structure, and are used to prepare correspondingly homogeneous products, in particular granules or oily dispersions, with reproducible levels of activity and resistance to environmental leaching after application onto agronomic surfaces. All the compositions and products object of the invention are water-free; in addition, due to their homogeneous structure, they are different from multiphasic or multi-structured products, e.g. coated cores, etc., which are accordingly not part of the invention. Accordingly, throughout this application, the terms “mix”, “mixed”, “mixing”, “mixtures” indicate the formation of homogeneous systems. Also the term “matrix” used herein indicates a homogeneous mixture of its components.
In the present description, numerical ratios among components are given indicated by the sign “:“ ; all of them are weight ratios of the relevant components, in the respective order as presented.
The invention is herein defined by various ranges, defined by a lower and upper limit and the expression, “between/ and” or “from/to”, equivalent and used indifferently for the purpose of the invention. Said upper and lower limits, all values between them, sub-ranges, and combinations thereof are part of the invention.
The term “oily” in the expression “oily agronomic active ingredient” indicates a lipophilic fluid product which is immiscible with aqueous solvents (for reference, distilled water at 20° C) and is freely miscible with organic solvents (for reference: methylene chloride at 20°C), having a kinematic viscosity of up to 100 mm2/sec at 20°C and ambient pressure, measured in standard conditions, cf. Eur. Pharmacopoeia 10.0 (2.2.9 Capillary viscosimeter method).
The term “oily agronomic active ingredient” defines any agronomic active ingredient which is “oily” as above defined; however, the term also extends to agronomic active ingredients which are not oily but are dissolved or dispersed in carrier oils; the carrier oils are "oily” as defined above, and remain such after dissolution therein of the agronomic active ingredient. In all the ratios described in this document, the weight of the “oily agronomic active ingredient” is meant as a whole, thus also including the carrier oil, when present.
Example of suitable carrier oils are vegetable oils like e.g. rape seed oil, sunflower oil, soy oil, olive oil and the like, modified vegetable oils e.g. alkoxylated sun flower or soy oil, or synthetic oils. More generally, carrier oils can be chosen within the following classes of compounds, provided that they are “oily” as defined above: (tri)glycerides like e.g. technical mixtures of mono, di and triglycerides of C6-C22 fatty acids, fatty acid alkyl esters e.g. methyl or ethyl esters of vegetable oils, fatty acid alkyl esters based on said C6-C22 fatty acids, etc., esters of linear C6-C22-fatty acids with branched alcohols, in particular 2- ethylhexanol, esters of C18-C38-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, linear or branched C6-C22- fatty alcohols, in particular dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (such as e.g. propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono-/di-/ triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as e.g., dicaprylyl carbonate (CetiolTM CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g., FinsolvTM TN), linear or branched, symmetrical or asymmetrical dialkylethers having 6 to 22 carbon atoms per alkyl group, such as e.g., dicapiylyl ether (CetiolTM OE), ring-opening products of epoxidized fatty acid esters with polyols.
The wax used in the invention can be conveniently selected from currently available waxes. According to their origin, the waxes are divided into three groups, i.e. natural, chemically modified or synthetic waxes; preferred are the natural or chemically modified waxes; most preferred are natural waxes.
(i) Natural waxes include plant waxes (e.g. candelilla wax, carnauba wax, japan wax, espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, etc.), animal waxes (e.g., beeswax, shellac wax, spermaceti, lanolin or wool wax, uropygial grease, etc.), and mineral waxes (e.g., ceresin, ozokerite or earth wax, etc.); particularly preferred are myrtle wax, rice wax, candelilla wax, mimosa wax, carnauba wax, soy wax, beeswax.
(ii) chemically modified waxes, including hard waxes (e.g., montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, etc.);
(iii) synthetic waxes, including polyalkylene waxes, polyalkylene glycol waxes (e.g., polyethylene glycol waxes), etc.
Generally for the present invention, esters of a long-chain alcohol (preferably C12 to C32) with a fatty acid (preferably C12 to C32) which are solid a room temperature can be regarded as waxes.
For further details on the concept of waxes, reference may be made, for example, to Rompp Chemielexikon, 10th edition, volume 6, 1999, Georg Thieme Verlag Stuttgart/New York, page 4906, entry heading: “Wachse” [Waxes] and also to the references cited therein, especially Cosm. Toil. 101, 49 (1986), and also DGF Einheitsmethoden [Standard methods], department M-Waxes and Wax Products, 7th supplement 05/ 1999, Stuttgart: Wissenschaftliche Verlagsgesellschaft, the aforementioned literature references being hereby incorporated in their entirety into the present specification by reference.
One typical aspect of the present compositions lies in that the weight ratio oily agronomic active ingredient to wax is comprised between 1.20: 1 and 2.80: 1; preferably it is comprised between 1.25: 1 and 2.70: 1; most preferably, it is comprised between 1.30: 1 and 2.65: 1. These ratios are reflected in any products obtained from the composition, in particular the granular products described herein. These ratios contribute to a correct balance of substances which is ideal from the point of view of sustained duration of action and resistance to leaching. The waxy substance, which is mainly responsible for adherence of the composition to the substrate to which it is applied, has the further advantage of being selectable from fully natural or nature- derived product, advantageously replacing any synthetic substances used in the prior art for the same purpose.
The oily agronomically active ingredient and the wax, considered as a whole, are herein indicated as “lipophilic matrix”: the attribute “lipophilic” derives from the presence of the wax and the oily agronomic active ingredient, both having lipophilic character; the term “matrix” highlights a structural function for the co-presence of these ingredients within the composition.
According to a first main embodiment, the above compositions further contain an inorganic carrier, which contributes to their structural performance. The inorganic carrier can be chosen from currently available ones. Examples thereof are: silica type materials such as sand, broken walnut hulls, argillaceous materials such as clay of the montmorillonite, kaolinite or other types, diatomaceous earths, zeolite, chabazite, clinoptilolite, leonardite, andalusite, ball clay, bentonite, calcium aluminate, feldspar, fused alumina, halloysite, mica, moler, mullite, zirconia, wallostonite, chamotte, perlite, carbon black, and other low density materials such as granulated corn cobs and other organic derivatives; talc, quartz, graphite, and many other inert materials with a variety of densities and other useful, relatively insoluble cores include agricultural minerals such as sulfur, gypsum, lime.
In the present compositions, the weight ratio of inorganic carrier to lipophilic matrix (i.e. the summed weight of oily agronomical active ingredient and wax) is comprised between 1.70: 1 and 2.40: 1. In more preferred embodiments it is comprised between 1.75: 1 and 2.35: 1; in most preferred embodiments, it is comprised between 1.80: 1 and 2.30: 1. The inorganic carrier has preferably an average particle size between 30 and 85 gm. These ratios and sizes are reflected in any products obtained from the composition, in particular the granular products described herein.
In particular, the combination of the ratio lipophilic ingredient:wax (from 1.20: 1 to 2.80: 1) with the ratio inorganic carrier: lipophilic matrix (from 1.70: 1 to 2.40: 1), obtains a rather fluid lipophilic matrix which is then mixed with a moderate excess of solid carrier, obtaining a “soft product” endowed with sustained release properties and good adhesivity properties once in contact with the plant or soil.
In general, any agronomic active ingredient can be used in the present invention. If they are “oily” as defined by the present application, they can be used as such; if not, they can be dissolved or suspended in a carrier oil, forming therewith the oily agronomic active ingredient in accordance with the invention.
In one embodiment, the oily agronomic active ingredient is one or more essential oils, used alone or, optionally, dissolved or dispersed in carrier oils. Without limitation, examples of essential oils are: aromatic plant extracts selected from the group consisting of extracts of Abies sibirica, Malpighia glabra, Achillea millefolium. Allium sativum, Medicago sativa, Aloe vera, Artemisia annua, Arnica Montana, Ocimum basilicum, Betula pendula, Betula pubescens, Calendula officinalis, Matricaria chamomilla, Chamaemelum nobile, Cinnamomum verum, Centella asiatica, Chelidonium majus, Syzygium aromaticum, Allium cepa, Equisetum arvense, Curcuma longa, Echinacea purpurea, Echinacea angustifolia, Eucalyptus globulus, Hypericum perforatum, Fucus vesiculosus, Glycine max, Glycyrrhiza glabra, Gentiana lutea, Lavandula angustifolia, Linen seed, Melilotus officinalis, Melissa officinalis, Punica granatum, Mentha piperita, Mentha spicata Vaccinium myrtillus, Origanum vulgaris, Orthosiphon stamineus, Urtica dioica, Olea europeae, Tabebuia impetiginosa, Plantago lanceolata, Hieracium pilosella, Pinus sibirica, Polypodium leucotoms, Citrus lemon, Citrus sinensis, Citrus paradisi, Quassia amara, Rheum Thais, Rosa canina, Rosmarinus officinalis, Ruscus aculeatus, Salix alba, Salvia officinalis, Salvia rosmarinus, Sesamus indicum,Camelia sinensis, Tilia tomentosa, Thymus vulgaris, Arctostaphylos uva-ursi, Valeriana officinalis, Solidago virgaurea, Loranthus europaeus, Zingiber officinalis.
Preferably, said aromatic plant extract is selected from the group consisting of extracts of Mentha piperita, Mentha Spicata, Thymus vulgaris, Salvia officinalis, Rosmarinus officinalis, Sesamus indicum, Syzygium aromaticum, Allium sativum, Citrus lemon, Cinnamomum verum, Origanum vulgaris, separately or in mixture.
Particularly preferred essential oils are: clove oil, neem oil, cinnamon oil, cedar oil, castor oil, geranium oil, lemongrass oil, mint oil, thyme oil, turmeric oil, Wintergreen oil, rosemary oil , anise oil, cardamom oil, chamomile oil coriander oil, cumin oil, dill oil, mint oil, parsley oil, lavender oil, basil oil, camphor oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil, grapefruit oil, lemon oil, mandarin oil, orange oil, pine needle oil, pepper oil, rose oil, sweet orange oil, tangerine oil, tea tree oil, tea seed oil, caraway oil, garlic oil, peppermint oil, onion oil, spearmint oil, terpenes, azadiractin, spynosyns, sesquiterpenes, oxygenated sesquiterpenes, phenyl propanoids.
In other embodiments, the agronomic active ingredient can be independently selected, for example, in one or more of the following classes of insecticides, fungicides, antimicrobials, nematicides, herbicides, semiochemicals. Mixtures of agronomic active ingredients belonging to the same class and/or to different classes can also be used.
The insecticides can be selected e.g. in the classes of: Acetylcholine esterase (AchE) inhibitors; Sodium channel modulators; Nicotinic acetylcholine receptor (nAChR) agonists; Nicotinic acetylcholine receptor allosteric activators; Chloride channel activators; Juvenile hormone mimics; Chordotonal organ TRPV channel modulators; Mite growth inhibitors; Microbial insecticidal proteins; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nicotinic acetylcholine receptor (nAChR) channel blockers; Inhibitors of chitin biosynthesis; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; electron transport inhibitors of Mitochondrial complex I, II or III; Voltage-dependent sodium channel blockers; Inhibitors of acetyl CoA carboxylase; Ryanodine receptormodulators; Chordotonal organ modulators; plant toxins and their derivatives.
Preferred insecticides and are selected among pyrethroids and among and neonicotinoids, such as Bifenthrin, Deltamethrin, Permethrin, Sumithrin, Tetramethrin, Transfluthrin, acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam.
The fungicides can be selected e.g. in the classes of: Respiration inhibitors; Sterol biosynthesis inhibitors; Nucleic acid synthesis inhibitors; Inhibitors of cell division and cytoskeleton; Inhibitors of aminoacid and protein synthesis; Signal transduction inhibitors; Protein inhibitors; Inhibitors with Multi Site Action; Cell wall synthesis inhibitors; Plant defences inducers.
Preferred fungicides are chosen among azoxystrobin, boscalid, carboxin, fenfuram, azaconazole cyproconazole , prothioconazole, difenoconazole, diniconazole, diniconazole-epoxiconazole, fenbuconazole, tebuconazole, imazalil, prochloraz, triflumizol, fenarimol, pyrifenox, triforine, valifenalate.
The antimicrobials can be selected e.g. in the class of antimicrobial peptides. Antimicrobial peptides are a class of small peptides that widely exist in nature and they are an important part of the innate immune system of different organisms and have a wide range of inhibitory effects against bacteria, fungi, parasites and viruses
Suitable antimicrobial peptides are described in Norine platform (see Norine: update of the nonribosomal peptide resource. Areski Flissi, Emma Ricart, Clementine Campart, Mickael Chevalier, Yoann Dufresne, Juraj Michalik, Philippe Jacques, Christophe Flahaut, Frederic Lisacek, Valerie Leclere and Maude Pupin Nucleic Acids Research, Nov. 2019, gkzlOOO, https: / / doi.org/ 10, 1093 /nar/gkz 1000), and represented e.g. by families A42867, A51568, A54145, A83850, ACV, AM-toxin, BT antibiotic, Calcium dependent antibiotic HC-toxin Kurstakin LP237 M43 MM OA7653 Orfamide PF 1022 aciculitin actinoidin actinomycin aeruginosin alamethicin amphibactin amphisin ampullosporin anabaenopeptilide anabaenopeptin andrimid anguibactin antiamoebin antipain apicidin apramide aquachelin arylomycin atroviridin aureobasidin aurilide avoparcin axinastatin axinellin azotobactin bacillibactin bacilysin bacitracin balhimycin bananamide barangamide beauvericin beauverolide bergofungin beta-lactam boletusin bottromycin brevianamide ca+-dependent lipopeptide callipeltin callynormine capreomycin carmabin cepaciachelin cephaibol ceratospongamide cereulide cervinin chlamydocin chloropolysporin chrysobactin chrysospermin coelichelin coronatine corrugatin corticiamide cupolamide cyanopeptolin cyclic depsipeptide cyclochlorotine cyclocinamide cyclolinopeptide cyclolithistide cyclonellin cyclosporin dysamide cyclotheonamide daptomycin decaplanin destruxin didemnin discobahamin discodermin dolastatin dysamide edeine emerimicin empedopeptin enduracidin enniatin enopeptin enterobactin entolysin eremomycin eurypamide feglymycin, fengycin ferintoic acid foroxymithine friulimicin fuscopeptin galacardin geodiamolide globomycin glycopeptide gramicidin gratisin guineamide gymnangiamide halicylindramide haligramide halipeptin harzianin helvecardin hemiasterlin heptaibin heptarhizins hymenamide hymenistatin hypomurocin isaridin isariin iturin jagaricin j aspamide kahalalide kapakahine kempopeptin keramamide konbamide koshikamide kulokainalide kulolide kulomo opunalide largamide leupeptin longibrachin lysobactin majusculamide malformin marinobactin microcystin microginin micromide microsclerodermin microspinosamide miraziridine montanastatin mozamide mycobacillin nagahamide nazumamide neosiphoniamolide neoviridogrisein nocardicin nodulapeptin nodularin nrp siderophore obyanamide onchidin orbiculamide oriamide orienticin ornibactin oscillamide , others ( not classified families such as disgocidine Chondrochloren Microsclerodermin cytochalasin E lydicamycin Myxoprincomide-c506 marynopyrrole E diaphorin cytochalasin K Prezeamine Aeruginosin 98-C methylpendolmycin Microsclerodermin M thailandamide A tryprostatin A Xenortide A neolymphostinol B Chivosazol Myxochromide SI chloramphenicol marynopyrrole C zeamine chaetoglobosins Xenortide D glandicoline B Curacin A marinopyrrole A lymphostin Phosphinothricintripeptide congocidine Rhabdopeptide 1 Melithiazol A cyclomarin D Ambactin eponemycin kirromycin fumiquinazoline C Nostophycin distamycin frontalamide B fumitremorgin B marynopyrrole D marthiapeptide A Xenortide marinopyrrole B Rhabdopeptide 3 4-deoxygaduso neolymphostin B calyculin A calyculinamide A thailandamide B demethoxyfumitremor gin C Rhabdopeptide 4 Notoamide A) , other lipopeptide (such as hectochlorin Echinocandin B bacillomycin D fusaricidin B Xenolindicin A surfactin xantholysin C alpha-lipomycin Arylomycin Thalassospiramide A xantholysin B) pallidin papuamide paracelsin peptaibolin peptaivirin perthamide petrosifungin phakellistatin phoriospongin phosphinothricin tripeptide plusbacin polydiscamide polymyxin pristinamycin I pseudacyclin pseudotheonamide pupukeamide putisolvin yoverdine pyrrolobenzodiazepine quinomycin ramoplanin scytalidamide serrawettin somamide stilboflavin stylopeptide stylostatin surfactin syringafactin syringomycin syringopeptin tentoxin theonegramide theonellamide theonellapeptolide theopalauamide tokaramide tolaasin trichobrachin trichorzin trichotoxin triostin tripropeptin tuberactinomycin tyrocidine uridylpeptide valinomycin vancomycin vibriobactin virginiamycin viscosin waiakeamide wainunuamide zervamicin
In one embodiment the antimicrobial peptides are beauvericins; cyclic depsipeptides, aureobasidins, cyclosporins.
The nematicides are chemical agents used to control parasitic worms such as roundworms and threadworms. In one preferred embodiment, they are selected from Oxamyl, Fluensulfone, Fluopyram, Ethoprop. In another preferred embodiment nematicides are clove oil, eugenol.
The herbicides can be selected e.g. in the classes of: lipid biosynthesis inhibitors; acetolactate synthase inhibitors; photosynthesis inhibitors; protoporphyrinogen-IX oxidase inhibitors; bleacher herbicides; enolpyruvyl shikimate 3 -phosphate synthase inhibitors (EPSP inhibitors); glutamine synthetase inhibitors; 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); mitosis inhibitors; inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); cellulose biosynthesis inhibitors; decoupler herbicides; auxinic herbicides; auxin transport inhibitors.
Preferred herbicides can be selected from protoporphyrinogen-IX oxidase inhibitors, enolpyruvyl shikimate 3 -phosphate synthase inhibitors, mitosis inhibitors and synthesis of very long chain fatty acids inhibitors (VLCFA inhibitors).
The semiochemicals can be selected e.g. in the classes of pheromones and kairomones. They can be selected from acyclic terpenes such as (Z,Z,Z)-3,6,9 triene C19-C21 hydrocarbon , (Z,Z)-6,9 diene C19-C21 hydrocarbon, their alcohols and esters, small ring terpenes such as limonene, sabinene, alpha terpineol, large ring terpenes such periplanone B,C,D,J , fused ring terpenes such as camphor, borneol, 3- carene, nepetaloctol, heterocyclic terpenes such asperillene, rose oxide. Preferably, they are selected from L-carvone, citral, (E,Z)-7,9- dodecadien- l-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7, 11, 13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, methyl eugenol, methyl jasmonate, (E,Z)-2, 13-octadecadien- l-ol, (E,Z)-2, 13-octadecadien- l-ol acetate, (E,Z)-3, 13-octadecadien- l-ol, ©-l-octen-3-ol, pentatermanone, (E,Z,Z)-3,8, 11 -tetradecatrienyl acetate, (Z,E)-9, 12-tetradecadien- l-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen- l-yl acetate, (Z)- l l- tetradecenal, (Z)- l 1-tetradecen- l-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract or mixtures thereof. The present compositions are useful for the production of improved granular products applicable in the agronomic field, characterized by excellent properties of sustained duration of action, and good resistance to environmental agents, in particular leaching by environmental agents like rain (rainfastness), wind, etc.
A further object of the invention is a process of producing the afore described compositions and granular products. The process is generally characterized by the steps of:
(a) mixing the oily agronomic active ingredient with the wax, at a temperature higher than the melting point of the wax, followed alternatively by:
(bl) cooling the product of step (a) to a temperature below the melting point of the wax and mixing the resulting product with the inorganic carrier, or
(b2) mixing the product of step (a) with the inorganic carrier and cooling the resulting product to a temperature below the melting point of the wax.
The resulting product can be further treated by conventional methods, for example by extrusion, to obtain a uniform granular formulation.
In this process, the weight ratio of oily agronomic active ingredient ingredient to wax is comprised between 1.20: 1 and 2.80: 1, and the weight ratio of inorganic carrier to lipophilic matrix [i.e. oily agronomic active ingredient + wax] is comprised between 1.70: 1 and 2.40: 1. Preferred sub-ranges for these ratios in the present process those described above in relation to the composition.
All mixing steps are performed until a homogeneous mixture of all the components subjected to mixing is obtained. The mixing is preferably performed by stirring.
In step (a), the mixing is preferably performed at a temperature at least 10°C higher than the melting temperature of the wax. The inorganic carrier has preferably an average particle size between 30 and 85 gm.
The mixing of the inorganic carrier with the lipophilic matrix can be conveniently performed at room temperature and in conventional mixers, obtaining a homogeneous mixture.
The present compositions, as obtained or obtainable by the above- mentioned process, have typically a solid or semi-solid consistence; from this product, uniformly structured granules can be obtained by conventional means such as extrusion through a small sized mesh, e.g. with mesh size comprised between 1 and 3 mm, e.g. 2 mm. The formed granular product is suitable for direct administration to the soil and/or plants, and does not require dissolution or dispersion in a water medium for subsequent irro ration. The lipophilic and greasy character of the product assures a strong adherence to the soil or plant, opposing to water leaching, wind dispersion, protecting the active ingredient from degradation and assuring its sustained release over time.
A further object of the invention are the agronomic granular products obtained from the above-described composition. These products are characterized by a high specific activity (i.e. ratio between the found activity of the active ingredient and its administered amount), enhanced properties of sustained duration of action and good resistance to environmental agents, such as leaching by rainwater (rainfastness), wind, etc. In particular, the granules are especially effective in high specific activity and sustained duration of action.
The invention also includes a method of applying, i.e. administering, the above-described granular agronomic formulation to a substrate. Said applying is typically performed by dispersing the corresponding granular product in its own solid form, i.e. not vehicled by liquids. The substrate of application is typically the soil or a plant or a plant parts in need thereof, with the advantage of the adhesivity of the product caused by its lipophilic and greasy character. Plant parts to which to granular product is applicable can be selected, without limitation from: leaves, bark, fruits, flowers, seeds or roots of plants and crops; specific examples thereof are cereals beans peas, fruit trees walnut, chestnut, almond, leafy vegetables, fruiting vegetables, root crops, processing crops, cucurbitaceous plants, pasture plants, lawn grasses, perfumery crops, ornamental plants, timber woods, etc.
According to a second main embodiment of the present invention, a composition is provided wherein the oily agronomic active ingredient and the wax are homogeneously mixed in a mutual weight ratio comprised between 1.20: 1 and 3.80: 1 (preferably between 1.50: 1 and 3.60: 1; more preferably between 1.80: 1 and 3.40: 1) and are not associated with the inorganic carrier. This composition, also defined herein as “lipophilic matrix”, is further mixed with a lipophilic solvent and a surfactant, as additional ingredients. In particular: i) the lipophilic solvent is added in a weight ratio to the oily agronomic active ingredient comprised between 1: 1 and 3: 1 (preferably between 1.2: 1 and 2.7: 1; more preferably between 1.3: 1 and 2.4: 1) and ii) the surfactant is added in a weight ratio to the oily agronomic active ingredient comprised between 0.20: 1 and 0.90: 1 (preferably between 0.24: 1 and 0.80: 1; more preferably between 0.28: 1 and 0.70: 1).
The resulting product (oily dispersion) is suitable for administration to an agronomic surface such as soil or plants, and is characterized by a sustained duration of action an excellent resistance to leaching by environmental factors.
In these compositions, the lipophilic solvent is additional to and different from the oily agronomical active ingredient and any components thereof: subject to this provision, the lipophilic solvent can be freely chosen with no criticality among any lipophilic solvents currently available. Accordingly, suitable lipophilic solvents can be chosen, without limiting the invention to one or more of the following:
Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6- C13-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stea rate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. esters of linear C6-C22-fatty acids with branched alcohols, in particular 2 -ethylhexanol, esters of C18-C38-alkyl hydroxy carboxylic acids with linear or branched C6-C 22-fatty alcohols, in particular dioctyl malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol and/or Guerbet alcohols), triglycerides based on C6-C10-fatty acids, liquid mono-/ di-/ triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2- C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as, for example, dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C6-C22-alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether, ring-opening products of epoxidized fatty acid esters with polyols.
Within the context of the present invention, preferred solvents are, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-C13- carboxylic acids with linear or branched C6-C22-fatty alcohols, such as e.g., myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate.
The other components of the composition according to the second main embodiment, i.e. the oily agronomically active ingredient components (agronomically active ingredient and, when present, the oil) and the wax can be freely chosen within the same groups of compounds, among the same specific compounds, in the same grade of preferences and associability, as exemplified and claimed in relation to the first main embodiment.
Accordingly, the second main embodiment can be described as a composition comprising, in homogeneous mixture: an oily agronomic active ingredient and a wax, having a weight ratio of oily agronomic active ingredient to wax comprised between 1.20: 1 and 3.80: 1 (preferably between 1.50: 1 and 3.60: 1; more preferably between 1.80: 1 and 3.40: 1), a lipophilic solvent and a wax.
In particular, in said composition, the lipophilic solvent is present in a weight ratio to the oily agronomic active ingredient comprised between 1: 1 and 3: 1 (preferably between 1.2: 1 and 2.7: 1; more preferably between 1.3: 1 and 2.4: 1), and the surfactant is present in a weight ratio to the oily agronomic active ingredient comprised between 0.20: 1 and 0.90: 1 (preferably between 0.24: 1 and 0.80: 1; more preferably between 0.28: 1 and 0.70: 1).
The invention is now described by the following non-limitative examples.
EXPERIMENTALS
Example 1 - Clove oil granules
2 kg of Clove oil [oily agronomic active principle] have been heated at 50°C in presence of paraffin wax (1,5 kg). Once obtained a clear solution, the mixture was let to cool at room temperature and added to 8kg of bentonite under stirring in a professional mixer. The paste was then extruded in a pilot extruder using 2mm diameter mesh.
Example 2 - Pyrethrum extract oily dispersion lkg of pyrethrum extract (50%) [oily agronomic active principle] is added to 2 kg of rapeseed oil [carrier oil]. The mixture has been heated at 50°C in presence of paraffin wax (1,5 kg). Once obtained a clear solution, the mixture was let to cool at room temperature. At this point, 4,5 kg of soybean methyl ester [lipophilic solvent] and 1 kg of the suitable alkyl sulfate surfactant have been added under agitation.
Example 3 - Difenoconazole oily dispersion
500 g of difenoconazole (98%) [agronomically active principle] is added to 2 kg of mandarin oil [carrier oil]. The mixture has been heated at 70°C in presence of beeswax (1 kg). Once obtained a clear solution, the mixture was let to cool at room temperature. At this point, 4,8 kg of sunflower oil methyl esters [lipophilic solvent] and 1, 1 kg of aminoacid surfactant have been added under agitation. Example 4 - Clove and mustard oil granules
1,2 kg of Clove oil [agronomically active principle] and 1,2 kg of mustard oil [agronomically active principle] have been heated at 50°C in presence of paraffin wax (1,8 kg). Once obtained a clear solution, the mixture was let to cool at room temperature and added to 8kg of mullite under stirring in a professional mixer. The paste was then extruded in a pilot extruder using 2mm diameter mesh.
Example 5 - Aspochracin oily dispersion
50 mg of Aspochracin [agronomically active principle] is added to 200 mg of mandarin oil [agronomically active principle] and 60 mg of carvacrol [agronomically active principle]. The mixture has been heated at 70°C in presence of beeswax (100 mg). Once obtained a clear solution, the mixture was let to cool at room temperature. At this point, 390 mg of propylene-glycol methyl esters [lipophilic solvent] and 200 mg of the suitable non-ionic block-copolymeric surfactants have been added under agitation.
Example 6 -Efficacy trials: nematicidal activity on tomato and cucumber (field trials)
6.1 Tomato
Plots of 25m2 of tomato seedlings (BBCH 12- 14) have been set up to evaluate the efficacy of the formulated products described in example 1 and 4 against nematodes. As control, a commercial reference product against nematodes was used.
The trial design is shown in table 1
Figure imgf000023_0001
Table 1
After 72 days (BBCH 65-67), the trial has been analyzed in term of efficacy respect to the control.
Results are reported in Table 2
Figure imgf000023_0002
Table 2
6.2 Cucumber
Plots of 25m2 of cucumber seedlings (BBCH 12- 14) have been set up to evaluate the efficacy of the formulated products described in example 1 and 4 against nematodes. As control, a commercial reference product against nematodes was used.
The trial design is shown in table 3
Figure imgf000024_0001
Table 3
After 43 days (BBCH 69-71), the trial has been analyzed in term of efficacy respect to the control. Results are reported in Table 4
Figure imgf000024_0002
Table 4
The results obtained in tables 4 and 2 show, for the formulations in accordance with the invention, excellent properties of duration of action and, therefore, of prolonged release of the active principle over time, of the order or even superior to commercial reference products, with the advantage of a natural and environmental-friendly wax-based composition.
Example 7 - Rainfastness of the products in vitro
The products of example 2,3 and 5 have been tested for rainfastness. A section of Parafilm® thermoplastic film (10X30 cm) is treated by spraying with 2mL of a solution obtained by diluting the product in water at 50% w / v.
The thermoplastic film section is allowed to dry at room temperature and the entire surface is then washed with 12mL of water using a standard spray system with 1mm nozzle. The thermoplastic film section after washing is dried and then treated with ethanol 98%. The collected solution is analyzed for the residual quantity of the products after washing by HPLC-MS
The results are highlighted in Table 5
Figure imgf000025_0001
Table 5
Example 8 - Rainfastness of the products in greenhouse
Plots of 5m2 of tomato seedlings (BBCH 13-29) have been set up to evaluate residuality of the products described in example 2 and 3 on the leaf.
As control, the same products not formulated are used at the same dose.
The trial design is shown in table 6
Figure imgf000025_0002
Table 6 The different products containing the respective active ingredient have been applied at a dosage of 2 L/ha by diluting the product in water sufficient to wet the culture well but limiting dripping (minimum 200 L/ha). After 4 hours the seedlings are sprinkled with water for 5 minutes to simulate a rain of 40 to 50 mm. The leaves have been let to dry. The leaves of each thesis, after drying, have been collected and analyzed to quantify the residual active ingredient.
The results are reported in table 7
Figure imgf000026_0001
Table 7
The results obtained in tables 5 and 7 show, for the formulations in accordance with the invention, excellent properties of rainfastness, of the order or even superior to commercial reference products, with the advantage of a natural and environmental-friendly wax-based composition.

Claims

1. Composition comprising, in homogeneous mixture: an inorganic carrier, an oily agronomic active ingredient and a wax, having a weight ratio of oily agronomic active ingredient to wax comprised between 1.20: 1 and 2.80: 1, and a weight ratio of inorganic carrier to [oily agronomic active ingredient + wax] comprised between 1.70: 1 and 2.40: 1.
2. The composition of claim 1, wherein the weight ratio of oily agronomic active ingredient to wax is comprised between 1.25: 1 and 2.70: 1.
3. The composition of claim 1, wherein the weight ratio oily agronomic active ingredient to wax is comprised between 1.30: 1 and 2.65: 1.
4. The composition of claims 1-3, wherein the oily agronomic active ingredient includes one or more essential oils.
5. The composition of claim 4, wherein the essential oils are selected among clove oil, neem oil, cinnamon oil, cedar oil, castor oil, geranium oil, lemongrass oil, mint oil, thyme oil, turmeric oil, Wintergreen oil, rosemary oil , anise oil, cardamom oil, chamomile oil coriander oil, cumin oil, dill oil, mint oil, parsley oil, lavender oil, basil oil, camphor oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil, grapefruit oil, lemon oil, mandarin oil, orange oil, pine needle oil, pepper oil, rose oil, sweet orange oil, tangerine oil, tea tree oil, tea seed oil, caraway oil, garlic oil, peppermint oil, onion oil, spearmint oil, terpenes, azadiractin, spynosyns, sesquiterpenes, oxygenated sesquiterpenes, phenyl propanoids.
6. The composition of claims 1-5, wherein the agronomic active ingredient includes one or more substances belonging to the classes of: insecticides, fungicides, antimicrobials, nematicides, herbicides, semiochemicals.
7. The composition of claim 6, wherein: (a) the insecticides are selected in the classes of: Acetylcholine esterase (AChE) inhibitors; Sodium channel modulators; Nicotinic acetylcholine receptor (nAChR) agonists; Nicotinic acetylcholine receptor allosteric activators; Chloride channel activators; Juvenile hormone mimics; Chordotonal organ TRPV channel modulators; Mite growth inhibitors; Microbial insecticidal proteins; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nicotinic acetylcholine receptor (nAChR) channel blockers; Inhibitors of chitin biosynthesis; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; electron transport inhibitors of Mitochondrial complex I, II or III; Voltage-dependent sodium channel blockers; Inhibitors of acetyl CoA carboxylase; Ryanodine receptormodulators; Chordotonal organ modulators; plant toxins and their derivatives;
(b) the fungicides are selected in the classes of: Respiration inhibitors; Sterol biosynthesis inhibitors; Nucleic acid synthesis inhibitors; Inhibitors of cell division and cytoskeleton; Inhibitors of aminoacid and protein synthesis; Signal transduction inhibitors; Protein inhibitors; Inhibitors with Multi Site Action; Cell wall synthesis inhibitors; Plant defences inducers;
(c) the antimicrobials are antimicrobial peptides;
(d) the herbicides are selected in the classes of: lipid biosynthesis inhibitors; acetolactate synthase inhibitors; photosynthesis inhibitors; protoporphyrinogen-IX oxidase inhibitors; bleacher herbicides; enolpyruvyl shikimate 3 -phosphate synthase inhibitors (EPSP inhibitors); glutamine synthetase inhibitors; 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); mitosis inhibitors; inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); cellulose biosynthesis inhibitors; decoupler herbicides; auxinic herbicides; auxin transport inhibitors;
(e) the nematicides are selected among Oxamyl, Fluensulfone, Fluopyram, Ethoprop, clove oil and eugenol. (f) the semiochemicals are selected in the classes of pheromones and kairomones.
8. The composition of claims 1-7, wherein the wax is selected from one or more among;
(i) Natural waxes, such as myrtle wax, rice wax, candelilla wax, mimosa wax, carnauba wax, soy wax, japan wax, espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax; animal waxes, such as beeswax, shellac wax, spermaceti, lanolin or wool wax, uropygial grease; mineral waxes such as ceresin, ozokerite or earth wax;
(ii) chemically modified waxes, such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes;
(iii) synthetic waxes, such as polyalkylene waxes, polyalkylene glycol waxes.
9. The composition of claims 1-8, wherein the inorganic carrier carrier has an average particle size between 30 and 85 gm.
10. The composition of claims 1-9, wherein the inorganic carrier is selected from: silica type materials such as sand, broken walnut hulls, argillaceous materials such as clay of the montmorillonite, kaolinite or other types, diatomaceous earths, zeolite, chabazite, clinoptilolite, leonardite, andalusite, ball clay, bentonite, calcium aluminate, feldspar, fused alumina, halloysite, mica, moler, mullite, zirconia, wallostonite, chamotte, perlite, carbon black, granulated corn cobs, talc, quartz, graphite, sulfur, gypsum, lime.
11. The composition of claims 1- 10, wherein the weight ratio of inorganic carrier to [oily agronomic active ingredient + wax] is comprised between 1.75: 1 to 2.35: 1 or between 1.80: 1 and 2.30: 1.
12. The compositions of claims 1- 11 in granular form.
13. Use of the composition in granular form of claim 12, for application to a plant and/or soil in an agronomic method of treatment.
14. Process to prepare the composition of claims 1- 12, comprising the steps of:
(a) mixing the oily agronomic active ingredient with the wax, at a temperature higher than the melting point of the wax, followed alternatively by:
(bl) cooling the product of step (a) to a temperature below the melting point of the wax and mixing the resulting product with the inorganic carrier, or
(b2) mixing the product of step (a) with the inorganic carrier and cooling the resulting product to a temperature below the melting point of the wax, wherein the weight ratio of oily agronomic active ingredient to wax is comprised between 1.20: 1 and 2.80: 1, and the weight ratio of inorganic carrier to [oily agronomic active ingredient + wax] is comprised between 1.70: 1 and 2.40: 1.
15. Process of claim 14, wherein the product of (bl) or (b2) is further processed to obtain granules.
16. Product obtained by the process of claims 14- 15.
17. Composition comprising, in homogeneous mixture: an oily agronomic active ingredient and a wax, at a weight ratio of oily agronomic active ingredient to wax comprised between 1.20: 1 and 3.80: 1, a lipophilic solvent and a surfactant.
18. The composition of claim 17 wherein the lipophilic solvent is in a weight ratio to the oily agronomic active ingredient comprised between 1: 1 and 3: 1, and the surfactant is in a weight ratio to the oily agronomic active ingredient comprised between 0.20: 1 and 0.90: 1.
19. The composition of claims 17- 18, wherein the oily agronomic active ingredient includes one or more essential oils.
20. The composition of claim 19, wherein the essential oils are selected among clove oil, neem oil, cinnamon oil, cedar oil, castor oil, geranium oil, lemongrass oil, mint oil, thyme oil, turmeric oil, Wintergreen oil, rosemary oil , anise oil, cardamom oil, chamomile oil coriander oil, cumin oil, dill oil, mint oil, parsley oil, lavender oil, basil oil, camphor oil, lemongrass oil, eucalyptus oil, fennel oil, ginger oil, grapefruit oil, lemon oil, mandarin oil, orange oil, pine needle oil, pepper oil, rose oil, sweet orange oil, tangerine oil, tea tree oil, tea seed oil, caraway oil, garlic oil, peppermint oil, onion oil, spearmint oil, terpenes, azadiractin, spynosyns, sesquiterpenes, oxygenated sesquiterpenes, phenyl propanoids.
21. The composition of claims 17-20, wherein the agronomic active ingredient includes one or more substances belonging to the classes of: insecticides, fungicides, antimicrobials, nematicides, herbicides, semiochemicals.
22. The composition of claim 21, wherein:
(a) the insecticides are selected in the classes of: Acetylcholine esterase (AChE) inhibitors; Sodium channel modulators; Nicotinic acetylcholine receptor (nAChR) agonists; Nicotinic acetylcholine receptor allosteric activators; Chloride channel activators; Juvenile hormone mimics; Chordotonal organ TRPV channel modulators; Mite growth inhibitors; Microbial insecticidal proteins; Inhibitors of mitochondrial ATP synthase; Uncouplers of oxidative phosphorylation; Nicotinic acetylcholine receptor (nAChR) channel blockers; Inhibitors of chitin biosynthesis; Moulting disruptors; Ecdyson receptor agonists; Octopamin receptor agonists; electron transport inhibitors of Mitochondrial complex I, II or III; Voltage-dependent sodium channel blockers; Inhibitors of acetyl CoA carboxylase; Ryanodine receptor-modulators; Chordotonal organ modulators; plant toxins and their derivatives;
(b) the fungicides are selected in the classes of: Respiration inhibitors; Sterol biosynthesis inhibitors; Nucleic acid synthesis inhibitors; Inhibitors of cell division and cytoskeleton; Inhibitors of aminoacid and protein synthesis; Signal transduction inhibitors; Protein inhibitors; Inhibitors with Multi Site Action; Cell wall synthesis inhibitors; Plant defences inducers;
(c) the antimicrobials are antimicrobial peptides;
(d) the herbicides are selected in the classes of: lipid biosynthesis inhibitors; acetolactate synthase inhibitors; photosynthesis inhibitors; protoporphyrinogen-IX oxidase inhibitors; bleacher herbicides; enolpyruvyl shikimate 3- phosphate synthase inhibitors (EPSP inhibitors); glutamine synthetase inhibitors; 7,8-dihydropteroate synthase inhibitors (DHP inhibitors); mitosis inhibitors; inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors); cellulose biosynthesis inhibitors; decoupler herbicides; auxinic herbicides; auxin transport inhibitors;
(e) the nematicides are selected among Oxamyl, Fluensulfone, Fluopyram, Ethoprop, clove oil and eugenol;
(f) the semiochemicals are selected in the classes of pheromones and kairomones.
23. The composition of claims 17-22, wherein the wax is selected from one or more among;
(i) Natural waxes, such as myrtle wax, rice wax, candelilla wax, mimosa wax, carnauba wax, soy wax, japan wax, espartograss wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax; animal waxes, such as beeswax, shellac wax, spermaceti, lanolin or wool wax, uropygial grease; mineral waxes such as ceresin, ozokerite or earth wax;
(ii) chemically modified waxes, such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes; (iii) synthetic waxes, such as polyalkylene waxes, polyalkylene glycol waxes.
24. The composition of claims 17-23, in the form of oily dispersion.
25. Use of the oily dispersion of claim 24, for application to a plant and/or soil in an agronomic method of treatment.
26. Process to prepare the composition according to claims 17-24, comprising the following steps:
(a) mixing the oily agronomic active ingredient with the wax, at a temperature higher than the melting point of the wax;
(b) cooling the product of step (a) to a temperature below the melting point of the wax;
(c) mixing the product of step (b) with a lipophilic solvent and a surfactant, to obtain an oily dispersion, wherein: the weight the weight ratio of oily agronomic active ingredient to wax is comprised between 1.20: 1 and 3.80: 1, preferably between 1.50: 1 and 3.60: 1, more preferably between 1.80: 1 and 3.40: 1.
27. The process of claim 26, wherein: the weight ratio of lipophilic solvent to oily agronomic active ingredient is comprised between 1: 1 and 3: 1, preferably between 1.2: 1 and 2.7: 1; more preferably between 1.3: 1 and 2.4: 1; and the weight ratio of surfactant to oily agronomic active ingredient is comprised between 0.20: 1 and 0.90: 1, preferably between 0.24: 1 and 0.80: 1; more preferably between 0.28: 1 and 0.70: 1.
PCT/EP2024/059138 2023-04-07 2024-04-04 Improved waxy delivery forms for oily agronomic active ingredients and method of preparation WO2024208945A1 (en)

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