• 专利附录
  • 专利说明
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    • 专利摘要:
    The invention relates to projectiles of paintball ball type containing insect pheromones, encapsulated in an aqueous formulation of oil-in-water emulsion type. These formulations are capable of releasing these pheromones in a prolonged manner. These projectiles have the particularity of containing the encapsulated aqueous pheromone formulation compatible with the envelope of the projectile composed of oxo-degradable polymer. The invention relates to the use of these projectiles for the treatment of trees against insect pests by projection and bursting of said projectile on the trunks of said trees.
    公开号:FR3041503A1
    申请号:FR1559087
    申请日:2015-09-25
    公开日:2017-03-31
    发明作者:Olivier Guerret；Samuel Dufour
    申请人:Melchior Material and Life Science France SAS；
    IPC主号:
    专利说明:

    OXODEGRADABLE PROJECTILES CONTAINING PHEROMONES Introduction
    The present invention relates to the manufacture and use of paintball ball projectiles containing pheromones such as processionary caterpillar pheromones encapsulated in an emulsion-type aqueous formulation. These formulations are capable of releasing these pheromones in a prolonged manner. These projectiles have the particularity of containing an encapsulated aqueous pheromone formulation compatible with the shell of the projectile composed of oxo-degradable or oxo-biodegradable polymer. Another object of the invention is the use of these innovative systems for the treatment of forests or orchards against insect pests via the technique of sexual confusion.
    PRIOR ART The use of pheromones for the control of insect populations in agriculture or forestry is well known to those skilled in the art. A pheromone is a chemical produced by an animal that is a stimulus for individuals of the same species or another species. Pheromones can therefore be produced either by living organisms or artificially by chemical synthesis.
    The principle of action of pheromone treatments is either to guide insects to an insect trap or to introduce sexual confusion by saturating pheromones with the antennae of insects that normally allow a male to find females (or the Contrast) (Chapter 4 edited by Richard L. Ridgway, Robert M. Silverstein, May N. Inscoe).
    In the case of arboriculture, the usual pheromone diffusion techniques are wick bottles, programmable sprays, or strips soaked with pheromones hanging from the branches. Examples include wick bottles such as those sold under the Rhynchotrak® or Rhyncopro® brand names, plastics (Cosmotrack®) or gels soaked in the substance containing the pheromones (eg US 20110014257 or US 8828374 B2), capsules porous plastics (eg BASF products sold under the Rak® brand) or programmable vaporizer technologies (US 2008/0184614, or Checkmate® product). These techniques, interesting as they are, have many defects including cost of implementation (which includes the installation and removal of diffusers) or their manufacturing cost. In addition, when it comes to silviculture, the issues of ease of installation become even more obvious because of the height of the trees and the difficulty of access to certain places. Other techniques have therefore been envisaged, such as the aerial spreading of microparticles (US Pat. No. 6,540,991), or the use of projectiles thrown into tree branches. These last techniques are promising but meet objections as to respect for the environment.
    Thus, as early as 1974, James C. Haie had the idea of using gun or rifle projectile launching systems to mark trees (US Pat. No. 3,788,298). Several proposals were then made to adapt this technique to the treatment of forests, with pesticides or pheromones, against their pests including the development of various types of projectiles: projectiles connected by a spring as in US Patent 8561343, projectile cartridges or explosives with one or two compartments as described in US 6772694B1 or US 200606518A1. Indeed, one of the major difficulties in designing projectiles adapted to a launcher such as a pistol or an airgun is that the "balls" must both be sufficiently resistant, chemically compatible with their contents (composition based on pheromones or pesticides) and easy rupture at the moment of impact. Thus, the projectiles used often consist of a gelatin envelope (patent US20020061325 A) which is not compatible with the pheromone compositions containing water (problem of softening the gelatin shell in the presence of a medium). watery which makes its projection impossible mechanically).
    However, the advantage of aqueous formulations for gradually releasing pheromones is important because they are compatible with the environment. If the matrix of micro particles is itself biodegradable, the entire system (envelope and aqueous formulation) is itself biodegradable which makes it suitable for use in the natural environment. Moreover, if another solvent than water was used, its evaporation in the air would induce an air pollution unsuitable for the intensive treatment of forests infested by defoliating insects for example.
    Some biodegradable envelopes have been studied in the past. Thus keratin has been proposed to form the envelope of projectiles containing a disinfectant in the case of the pine processionary (patent WO 2008/065218). However, besides no example of aqueous content is provided, recent work (including those of INRA), show that keratin is difficult to transform industrially to produce projectiles that could be filled with an aqueous formulation pheromone.
    Furthermore, in the patent FR 200951799, D. Delhaye describes a system of paintballs characterized in that their envelopes are composed of an oxobiododegradable polymer. This material is a polymer that contains transition metals which, under the combined action of oxygen and V. radiation, degrade the polymer into micro pieces that in the case of polyolefins will become biodegradable. Such envelopes are designed to convey fertilizers, insecticidal or phytosanitary products in liquid form and compatible with the envelope material.
    Existing solutions are unsatisfactory for the dispersion of pheromones that are not compatible with oxodegradable materials. In addition, a liquid formulation causes splashing at the time of impact and bursting and a significant loss of active material. The inventors have therefore designed aqueous pheromone formulations that are compatible with the envelopes of oxobiododegradable polymer projectiles and which allow to release insect pheromones for several months, which makes it possible to induce the sexual confusion of insect pests of forests or trees. orchards.
    DESCRIPTION OF THE INVENTION
    The applicant has therefore developed a new type of projectile capable of treating trees against insect infestations shown in FIG.
    Thus, in a first embodiment, the present invention relates to a projectile comprising an envelope and a filling characterized in that the envelope comprises an oxodegradable thermoplastic polymer or copolymer and in that the filling consists of an aqueous emulsion type formulation. wherein the aqueous phase comprises a gelling agent and the fatty phase comprises a matrix consisting of a mixture of oil and / or wax and pheromone.
    In a second embodiment, the projectile according to the invention is characterized in that the oxodegradable thermoplastic polymer or copolymer of the envelope is chosen from the group consisting of oxodegradable polyolefins.
    Preferably, the oxodegradable thermoplastic polymer or copolymer is chosen from the group consisting of oxodegradable polyethylene and oxodegradable polypropylene.
    In another embodiment of the present invention, the projectile is characterized in that the emulsion of the aqueous formulation comprises 20 to 70% by weight of aqueous phase and 80 to 30% of fat phase.
    The projectile according to the invention, in another embodiment of the invention is characterized in that the gelling agent is selected from the group consisting of cellulose ethers, polyurethanes and copolymers of (meth) acrylic acid and ethyl acrylate.
    In particular, the projectile according to the invention is characterized in that the gelling agent is a copolymer of (meth) acrylic acid and ethyl acrylate comprising: between 30 and 40% by weight of methacrylic acid between 45 and 60% by weight of ethyl acrylate between 5 and 20% by weight of a macromonomer of general formula (I):
    where m is an integer between 1 and 40, preferably between 10 and 30 and where R is a group of general formula CnH2n + 1 in which n is an integer between 9 and 25, preferably between 10 and 20 and still preferably equal to 12; the pH of the aqueous phase is between 5 and 8.
    In a particular embodiment of the invention, the projectile according to the invention is characterized in that the fatty phase comprises from 0 to 90% by weight of wax, particularly from 10 to 80% by weight of wax, from 0.1 to 25% by weight of pheromone and 0 to 90% by weight of oil, particularly 10 to 80% by weight of oil and 0 to 0.8% by weight of stabilizer, anti-oxidant and anti-UV
    According to another embodiment of the invention, the pheromone of the projectile has been chosen from the group of fat-chain insect pheromones, in particular a sex pheromone of pine processionary moths, oak processionary moths, and moths. boxwood, bombyx and carpocapses. It is also another object of the present invention to provide a projectile as defined above, characterized in that the envelope / filling mass ratio is between 1/20 and 1/200.
    Also in one embodiment of the invention, the projectile is characterized in that the thickness of the envelope is between 50 and 500 pm, preferably between 80 and 250 pm.
    In a particular embodiment of the invention, the projectile is characterized in that it is a sphere of diameter between 0.5 and 5 cm, preferably between 1 and 3 cm.
    In order to ensure satisfactory impact spreading, the projectile according to one of the variants of the invention is characterized in that the viscosity of the aqueous formulation of the filling is between 1000 and 15000 centipoise at 25 ° C, particularly between 2000 and 10000 centipoise at 25 ° C.
    In another embodiment, the projectile according to the invention is characterized in that the mass ratio oil and / or wax / pheromone in the fatty phase is between 70/30 and 99.5 / 0.5, more particularly between 80/20 and 98/2.
    The present invention also relates to the use of a projectile according to one of the embodiments described here for the protection of a parcel of trees against a pest insect characterized by the fact that the projectile is projected and bursts on the trunk of trees of the plot to be protected. In particular, the projectile is projected with sufficient force to burst the envelope and adhere all or part of the filling on the trunk. The use of a projectile according to the invention as described is also characterized in that the insect pest is selected from the group consisting of the butterfly of the pine processionary, the moth of the processionary oak, the borer of the boxwood, bombyx and carpocapses.
    Finally, in a particular embodiment of the invention, the use of the projectile as described is characterized in that said projectile is projected and bursts at the height of the canopy
    Thus the projectile according to the invention comprises an envelope and a filling and is characterized in that the envelope comprises an oxodegradable thermoplastic polymer or copolymer and the filling comprises an aqueous formulation of "oil-in-water" emulsion type in which the aqueous phase comprises a gelling agent and the fatty phase comprises a matrix consisting of a mixture of oil and / or wax and pheromone.
    The aqueous formulation of the projectile is able to slowly release pheromones and resist washing by the weather, to control the behavior of insects or animals.
    The projectile may have a spherical, ovoid, cylindrical or conical shape or any other molded shape. Preferably the projectile is a sphere of diameter between 0.5 and 5 cm, particularly between 1 and 3 cm in diameter. The shell of the projectile is made of an oxodegradable or oxobiododegradable thermoplastic polymer or copolymer, preferably of oxodegradable or oxobiododegradable polyethylene or polypropylene. The term "thermoplastic" refers to a material that softens repeatedly when heated above a certain temperature, but below it becomes hard again. Such a material will therefore always reversibly retain its initial thermoplasticity. The term "oxodegradable" or "oxobiododegradable" refers to a polymeric material that can degrade biologically in nature, having previously undergone abiotic oxidative degradation under the combined effects of heat and UV, by oxidation of the bonds. carbon-hydrogen which causes a decrease in the molecular weight of the material. The oxidized material in the presence of microorganisms is then converted to CO2, water and non-sterile biomass, without generating toxic residues
    The filling of the projectiles according to the invention comprises, or consists of, an aqueous formulation which allows the pheromones to be released slowly. This aqueous formulation comprises, or consists of, an oil-in-water emulsion which comprises from 20 to 70% by weight of aqueous phase and from 80 to 30% by weight of a dispersed fatty phase comprising, or consisting of, a matrix based on natural wax and / or biodegradable natural oil in which is incorporated the pheromone or pheromones to control the behavior of insects.
    The stability of the emulsion of the aqueous phase is ensured by the presence of a gelling agent, or rheological modifying agent, water-soluble. The gelling agent, or rheology modifying agent, contributes to increasing the viscosity of the aqueous filling phase so that it does not scatter at the time of the projectile burst upon impact. The nature of the water-soluble gelling agent is not critical in being from the moment when it is compatible with the desired viscosity and with the pheromone contained in the fatty phase. The gelling agent or water-soluble rheology modifying agent can be chosen from polysaccharides or else from the group comprising cellulose ethers, polyurethanes, or HASE type copolymers.
    As cellulose ether, mention may be made of methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose.
    It is recalled that the polymers of HASE type: (hydrophobically modified alkali swellable emulsion) are copolymers of (meth) acrylic acid and alkyl acrylate produced by radical polymerization in emulsion which have the property during their neutralization by a base such as sodium hydroxide or ammonia to become water-soluble and to modify the rheology of water, but whose composition also comprises hydrophobic macromonomers of general formula:
    Where m is an integer, between 1 and 40, in general greater than 5 and where R is a group of general formula CnH2n + i in which n is an integer of between 10 and 30, especially between 9 and 25, more preferably between 10 and 20. They also have the ability to modify the rheology of the aqueous solution.
    They are prepared according to methods well known to those skilled in the art using a mercaptan chain transfer agent.
    The amount of water-soluble gelling agent in the aqueous phase may be between 5% by weight and 20% by weight. In a particular manner between 5 and 10% by weight of the aqueous phase. The amount of this water-soluble gelling agent can be adjusted according to its nature and its gelling capacities and in order to obtain the desired viscosity for the aqueous projectile filling formulation according to the invention.
    Preferably, the gelling agent is an acrylic copolymer, in particular a HASE-type acrylic copolymer, and is characterized in that it contains: between 30 and 40% by weight of methacrylic acid, between 45 and 60% by weight; weight of ethyl acrylate, - Between 5% and 20% by weight of a macromonomer of general formula (I):
    Where m is an integer between 1 and 40, preferably between 10 and 30 and where R is a group of general formula CnH2n + 1 in which n is an integer between 9 and 25, preferably between 10 and 20 and more preferably equal to 12.
    In the case of implementation of an acrylic copolymer, in particular an HASE type acrylic copolymer as defined above as a water-soluble gelling agent, its amount in the aqueous phase may be between 5 and 15% by weight, more particularly between 5 and 10% by weight. In order to obtain the desired viscosity, the pH of the aqueous phase will be between 5 and 8, particularly between 6 and 8, in order to ensure the gelation of this copolymer and to reach the desired viscosity.
    The dispersed fatty phase of the emulsion included in the aqueous formulation of the projectile filling according to the invention comprises from 10 to 90% by weight of wax, particularly from 60 to 80% by weight of wax, and from 10 to 90% by weight of wax. oil, particularly 8 to 35% by weight of oil, 0.1 to 25% by weight of pheromone, particularly from 0.5 to 20% by weight of pheromone, and from 0 to 0.8% by weight, particularly from 0.1 to 0.5% by weight. stabilizer weight.
    By "wax" is meant in the sense of the invention, a lipophilic compound, solid at room temperature (about 25 ° C) and atmospheric pressure (760 mm Hg). The waxes that may be used in a composition according to the invention may be chosen from waxes of animal, vegetable, mineral or synthetic origin and mixtures thereof. In particular, it is possible to use hydrocarbon-based waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candelila wax, jojoba wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, wax from Japan and sumac wax, montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters. There may also be mentioned waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains,
    linear or branched, C8-C32. Among these, there may be mentioned hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di-tetrastearate ( trimethylol-1,1,1 propane). It is also possible to use the waxes obtained by transesterification and hydrogenation of vegetable oils, such as castor oil or olive oil, such as the waxes sold under the names Phytowax ricin 16L64® and 22L73® and Phytowax Olive 18L57 by the company Sophim.
    By "oil" is meant a non-aqueous compound, immiscible with water, liquid at room temperature (about 25 ° C) and atmospheric pressure (760 mm Hg). The oil according to the invention may be chosen from vegetable oils. In particular, the oil according to the invention will be chosen from the group consisting of sunflower oil, peanut oil, soybean oil, rapeseed oil, corn oil, olive oil, grape oil, walnut oil, linseed oil, palm oil, coconut oil, argan oil, avocado oil, l almond oil, hazelnut oil, pistachio oil, rice oil, cottonseed oil, wheat germ oil, sesame oil, or mixtures thereof. Preferably, the oil is chosen according to the crop that is to be protected from insect pests, particularly lepidopterans.
    A stabilizer, or a mixture of stabilizers, anti-oxidant and / or anti-UV, may be contained in the filling of the projectiles according to the invention in order to preserve the components of the fatty phase, in particular the pheromone (s) of the oxidation and / or UV. The stabilizer may be selected from the group consisting of n-butyl-4-hydroxybenzoate (BHB), tocopherol, tert-butyl-hydroquinone (TBH), n-propyl gallate (PG), t-butyl-hydroxyanisole ( BHA), para-methyl-hydroxy-benzoate (MHB), N, N-dietyl-toluamide (DT), t-butyl-5-hydroxy-toluene (BHT) and β-thioglycerine (TG), nitroxides and alkoxyamines and mixtures thereof. The stabilizer or stabilizers make it possible to preserve the oil, the wax and / or the pheromone from oxidation and / or UV radiation.
    The pheromone (s) contained in the projectiles according to the invention are particularly pheromones of insects, more particularly pheromones of insects with a fatty chain. More particularly, it is pheromones of lepidopterous fatty chain. In particular, the projectiles according to the invention contain sexual pheromones of Lepidoptera. The sex pheromones of insects such as lepidopterans are characterized in that they are composed of mixtures of unsaturated fatty chain molecules with alcohol, ester or aldehyde endings.
    As pheromone contained in the projectiles according to the invention include the pheromones of the moths, carpocapses pests of trees such as box, chestnut, walnut, apple, pear. More particularly, the pheromone may be a sexual pheromone of pine and oak processionary butterflies. Known for their way of moving in single file, the larvae nest in the needles of various species of pines or in the leaves of oaks, causing a significant weakening of the trees. A common point with these pests is that butterflies move in the canopy of trees and it is one of the advantages of the invention to be able to place pheromone scattering points in trees at heights up to several meters without need to carry heavy equipment such as ladders or nacelles. The casing of the projectiles according to the present invention provides a mechanical resistance during storage, handling and during projection, for example using a pneumatic gun paintball type, and also by its rupture during the impact on a hard support such as the trunk of a tree, the bursting of the projectile and the release of the filling. The mass ratio between envelope and filling can be chosen to favor either the mechanical strength or the ease of bursting at impact and this according to the size of the projectile, the nature of the material of the envelope and the nature of the formulation of filling. In this context, the nature of the material constituting the envelope and its dimensional characteristics as well as the viscosity of the filling are such that the impact caused by a projectile on a hard surface causes the envelope to burst and to spread out. filling formulation avoiding splashing. In particular, the envelope / fill weight ratio may be between 1/20 and 1/200. The thickness of the shell of the projectiles according to the invention will depend on the size of the projectile, the envelope / filling mass ratio, the viscosity of said filling and also the nature of the oxodegradable thermoplastic material. The thickness of the envelope may thus be between 50 and 500 μm, particularly between 80 and 250 μm, and even more particularly between 100 and 200 μm, for example. By way of example, for a spherical projectile whose shell material is an oxodegradable thermoplastic polymer or copolymer such as oxodegradable polypropylene, of the order of 1.75 cm in diameter, the thickness of the envelope is of the order of 120 μm.
    Typically, a method of manufacturing projectiles according to the invention corresponds to that described in WO2014016510 and comprises the following steps: receiving two sections of oxodegradable thermoplastic film, each pan comprising at least one column of cavities formed; approximation of the two faces to match the respective cavities of each pan and plating of the panels by pairs of bars that successively pinch the sides on either side of the pairs of columns of cavities, filling the pocket defined between two pairs of bars by the filling formulation to fill the cavities and weld sections around the cavities to form the projectiles.
    In addition to its role as a stabilizer, the gelling agent, or rheology modifier, makes it possible to control the viscosity of the filling formulation. During the manufacture of the projectiles, the aqueous filling formulation must be sufficiently liquid to allow the projectiles to be filled at high rates. When impacting a trunk, it must be sufficiently viscous to ensure the formation of a film of sufficient thickness.
    The viscosity of the aqueous formulation for filling the projectile according to the invention is chosen so as to be sufficiently low so as to allow easy filling of the cavities of the projectiles during their manufacture, but high enough to limit the splashing at the moment of bursting. of the projectile during the impact of the latter on a hard surface, in particular a trunk. The gelling agent and the amounts of this agent and the conditions specific to its nature make it possible to determine the viscosity of the aqueous filling formulation. Thus, in the case of using copolymers and polymers of the HASE type, their gelation being determined by the pH, the pH of the aqueous phase will be between 5 and 8, particularly between 6 and 8, in order to gel said polymer. Indeed, the projectiles according to the present invention being particularly intended for the application of pheromonal composition at tree trunks, if the viscosity of the filling formulation is too low, splashes are generated at the time of the projectile bursting. impact, and a significant portion of the formulation may be lost and fall back to the ground.
    The Brookfield viscosity of the aqueous filling formulation is thus between about 1000 and about 15000 Centipoises, at 25 ° C, particularly between 2000 and 12000 centipoise, at 25 ° C, more particularly between 2500 and 10000 centipoises, at 25 ° C. The Brookfield viscosity of the aqueous fill formulation can be measured using a Brookfield viscometer consisting of applying a force of motion to a product - the aqueous formulation - by rotating at a fixed speed, a moving object. fixed size immersed in said product. The resistance of the product to the rotational movement of the moving body is recorded with the aid of an internal spiral spring and then converted into a viscometric unit, for example centipoise. By way of illustration, the viscosity of the aqueous projectile filling formulation according to the present invention may be established in a range corresponding to that ranging from a liquid honey to a crystallized honey, a mayonnaise or a chocolate spread by example. The adjustment of the wax and / or oil / pheromone ratio in the matrix of the fatty phase of the emulsion of the aqueous filling formulation depends on the solubility of the pheromones in the oil + wax mixture. This ratio may vary between 70/30 and 99.5 / 0.5, more particularly between 80/20 and 98/2, more particularly around 75/25, for example. The projectiles according to the invention are projected against the tree trunks by means of a compressed air system. The bursting of the projectile causes the spread of the aqueous formulation which forms a film on the surface of the trunk. The slow release of the pheromone through the film thus formed then makes it possible to control the behavior of the insects.
    Preferably, the insects targeted by this technology are forest pests or orchards such as the pine or oak processionaries, the boxworm or the bombyx, the carpocapses (apple, pear, chestnut, walnut ...). The projection of the projectiles according to the invention makes it possible to create in a forest or a tree area as many pheromone diffusion points as impacts realized. A high density of impacts combined with the controlled release of the pheromone by each diffuser creates a pheromone cloud that prevents the insect's reproductive cycle from proceeding properly. This disturbance reduces the population of pests and thus preserves the trees from the damage they cause. The impacts will be located preferentially at the level of the canopy and their number will be between 100 and 1000 per hectare. The advantage of the technique developed in this invention is to allow the treatment of large sylvan surfaces at a controlled cost while using only biodegradable components containing no other organic volatile pheromone itself.
    FIG. 1 represents a schematic view of a projectile according to the invention in which (1) represents the shell of the projectile made of oxobiododegradable thermoplastic material, (2) represents the particles containing a mixture of pheromone in a matrix based on wax and and / or oil and (3) represents the aqueous phase containing the gelling agent, or rheology modifying agent
    Figure 2 shows the detection of the degradation of the pheromone of the boxworm in the presence of an oxobiododegradable polymer.
    Figure 3 shows an example of projection of the projectiles on pins illustrating the interest of the system that allows to deposit multiple diffusers effortlessly. EXAMPLES:
    Materials:
    Pheromones used in silviculture are either purchased from industrial manufacturers or manufactured by M2i Development (Lacq, France) according to known methods. In the case of the products synthesized by M2i Development, their characterizations are validated by a comparative analysis with a reference sample in gas phase chromatography.
    Example 1 (excluding the invention): incompatibility of the pure pheromone in direct contact with oxo-biodegradable materials.
    The sexual pheromone of Boxwood Moth is the mixture of Z and E-11 hexadecenal in a 5: 1 ratio.
    A paint-ball projectile casing made of an oxo-biodegradable polyolefin is cut into small pieces on the order of 2 to 5 mm 2. The chips thus obtained are placed in a reactor containing a magnetic stirrer. The reactor is placed under nitrogen. 100 mg of the hexadecenal mixture described above are added to the chips and agitation is maintained until the liquid has been completely absorbed by the chips.
    Copals are then separated into two parts:
    The first half is stored in an aluminum bag under nitrogen (control). The second half is placed in a transparent cup closed under air to the light. Chips are regularly analyzed by gas phase chromatography. The evolution of the pheromonal mixture is reported in the following graph (Figure 2):
    It can be seen in FIG. 2 that the oxo-biodegradable polyolefin decomposes the pheromone mixture in the presence of oxygen when it is in direct contact with the polyolefin. Amongst other things, the appearance of hexadecenoic acid produces oxidation of pheromone. This example illustrates the problem of the compatibility of pheromones with oxobiodegradable polymers and the importance of protecting the pheromone in an emulsion as illustrated in the present invention.
    Example 2: Manufacture of aqueous formulations containing pheromones
    The acrylic rheology modifiers used in the formulations are HASE type acrylic copolymers supplied by Coatex (Rheotech® range, France).
    The HASE 1 copolymer used for the exemplifications consists of: 35.5% by weight of methacrylic acid, 52.4% by weight of ethyl acrylate, 12% by weight of a macromonomer of formula (I) in where m = 30 and n = 12.
    General protocol for manufacturing the aqueous formulation containing pheromones:
    Constituents of the formulation:
    Aqueous phase: HASE1 H20 rheological modifier
    10% NaOH
    Solution 1 Wax / oil
    Stabilizing pheromone (BHT)
    Solution 2 H3P04 (4%)
    Operating mode:
    Solution 1 is prepared by melting at 70 ° C., in a jacketed reactor 41 equipped with a mechanical stirrer (IKA) and a standard anchor or Impeller stirring rod, the beeswax mixture, sunflower oil, pheromone and stabilizer (BHT). The internal temperature in the reactor must be higher than the melting temperature of the wax.
    In a second jacketed reactor (201), provided with a mechanical stirrer (IKA) and a standard anchor or Impeller stirring rod, with stirring, the aqueous phase is prepared by charging the water, the soda and the rheological additive. This mixture is brought to a temperature above the melting point of the wax.
    When the solution 1 is melted, it is added, dropwise, to the aqueous phase using a Watson-Marlow pump (rotational speed 200) in about 5 '.
    In order to adjust the viscosity of the prepared formulation, solution 2 (phosphoric acid) is finally added dropwise at 15 ° with a temperature in the jacket of 35 ° C. The medium is stirred for 5 minutes before being cooled and brought to room temperature
    A controlled release aqueous formulation for the pine processionary plant
    The preparation of the pine processionary pheromone aqueous formulation was carried out according to the above general procedure with the amounts of reagents presented below.
    Example 3 Manufacture of Projectiles According to the Invention Using the Formulations of Example 2
    The projectiles according to the invention, of the paintball ball type, were manufactured by Polytek according to the process described in patent WO 2014016510 A1 and in the present description. The material used is an oxo-biodegradable polypropylene. The method comprises providing two films of similar polymeric material (oxo-biodegradable polypropylene). The filling composition as described above is made available. The films are arranged in an encapsulation unit comprising two molding drums which each comprise a cylinder in which a plurality of hemispherical cavities are formed, said
    drums are arranged so that their axes are parallel and their cylinders contiguous, said films scroll continuously in the encapsulation unit so as to arrive tangentially on said cylinders. The films are transformed into capsule portions of substantially hemispherical shape by counter-rotating rotation of said rolls of the molding drums. The filling composition is introduced into said capsule portions which are joined and closed to form the filled envelopes of the pheromonal composition. The diameter of the substantially spherical projectiles obtained is 1.75 cm (caliber 68).
    Example 4 Projection of Projectiles of Example 3 on Trees
    The transfer of material is measured on 10 trunks according to the following protocol:
    After 24 hours (time necessary to evaporate the water), the dry deposit is scraped off on the trunks, then each sample is dissolved in hot heptane and filtered in order to remove solid particles from the trunk or residues. of the envelope. The heptane is evaporated under reduced pressure and then the residue is weighed, which corresponds to the amount of material transferred on impact. This mass is then reported to the theoretical mass of matrix and pheromone contained in each projectile (1.01g).
    The results are as follows:
    On average 88.2% transfer. This demonstrates that the filling of the projectiles according to the invention is almost completely retained on the support and that there is only very little loss at the time of the bursting of the projectiles during the impact on the trunks.
    Example 5: Trial of sexual confusion in a piece of maritime pine.
    500 projectiles containing 1.01 g of oil / wax formulation loaded with 10% of (Z) -13-Hexadecen-11-yn-1-ol acetate, pheromone of sex attraction of the butterfly of the pine processionary, dispersed in 1.2 g d Water and containing 3% by weight of Hase 1 were prepared according to Example 3.
    The 500 projectiles were fired on the pines of a plot of 5 ha at a rate of 100 projectiles per hectare at a height between 2m50 and 5m. The mesh of the shots tends to respect a shooting every 10m according to the density of trees (figure 3).
    To follow the evolution of the population on site, Mastrap L @ type pheromone traps were placed every 10 m in the middle of the plot. 10 other traps were distributed on the periphery of the plot (25 m from it). The results are as follows:
    Table 2: Number of catches for the ten traps of each type (these numbers indicate the number of new catches)
    This example shows the effectiveness of the sexual disruption protection system according to the invention in the butterfly protection of the pine processionary.
    In addition, during the test, several thunderstorms sprayed the plot, which validated the resistance of the films deposited on the trunks during the treatment period.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    A projectile comprising an envelope and a filling characterized in that the envelope comprises an oxodegradable thermoplastic polymer or copolymer and in that the filling consists of an aqueous formulation of "oil-in-water" emulsion type in which the aqueous phase comprises an agent gelling agent and the fatty phase comprises a matrix consisting of a mixture of oil and / or wax and pheromone.
    [2" id="c-fr-0002]
    2. Projectile according to claim 1, characterized in that the oxodegradable thermoplastic polymer or copolymer of the envelope is selected from the group consisting of oxodegradable polyolefins.
    [3" id="c-fr-0003]
    3. Projectile according to claim 2, characterized in that the oxodegradable thermoplastic polymer or copolymer is selected from the group consisting of oxodegradable polyethylene and oxodegradable polypropylene.
    [4" id="c-fr-0004]
    4. Projectile according to one of claims 1 to 3, characterized in that the emulsion of the aqueous formulation comprises 20 to 70% by weight of aqueous phase and 80 to 30% of fat phase.
    [5" id="c-fr-0005]
    5. Projectile according to one of claims 1 to 4, characterized in that the gelling agent is selected from the group consisting of cellulose ethers, polyurethanes and copolymers of (meth) acrylic acid and acrylate. 'ethyl.
    [6" id="c-fr-0006]
    6. Projectile according to one of claims 1 to 5 characterized in that the gelling agent is a copolymer of (meth) acrylic acid and ethyl acrylate comprising: between 30 and 40% by weight of methacrylic acid between 45 and 60% by weight of ethyl acrylate between 5 and 20% by weight of a macromonomer of general formula (I):

    where m is an integer between 1 and 40, preferably between 10 and 30 and where R is a group of general formula CnH2n + 1 in which n is an integer between 9 and 25, preferably between 10 and 20 and still preferably equal to 12; the pH of the aqueous phase is between 5 and 8.
    [7" id="c-fr-0007]
    7. Projectile according to one of claims 1 to 6, characterized in that the fatty phase comprises 0 to 90% by weight of wax, particularly 10 to 80% by weight of wax, 0.1 to 25% by weight of pheromone and from 0 to 90% by weight of oil, particularly from 10 to 80% by weight of oil and from 0 to 0.8% by weight of stabilizer.
    [8" id="c-fr-0008]
    8. Projectile according to one of claims 1 to 7, characterized in that the pheromone is selected from the group of pheromones of fat-chain insects, in particular a sex pheromone pine processionary butterflies, butterflies processionaries of the oak, boxwood moth, bombyx and carpocapses.
    [9" id="c-fr-0009]
    9. Projectile according to one of claims 1 to 8, characterized in that the mass ratio envelope / filling is between 1/20 and 1/200.
    [10" id="c-fr-0010]
    10. Projectile according to one of claims 1 to 9, characterized in that the thickness of the casing is between 50 and 500 pm, preferably between 80 and 250 pm.
    [11" id="c-fr-0011]
    11. Projectile according to claims 1 to 10, characterized in that it is a sphere of diameter between 0.5 and 5 cm, preferably between 1 and 3 cm.
    [12" id="c-fr-0012]
    12. Projectile according to one of claims 1 to 11, characterized in that the viscosity of the aqueous formulation of the filling is between 1000 and 15000 centipoise at 25 ° C, particularly between 2000 and 10000 centipoise at 25 ° C.
    [13" id="c-fr-0013]
    13. Projectile according to one of claims 1 to 12, characterized in that the mass ratio oil and / or wax / pheromone in the fatty phase is

    between 70/30 and 99.5 / 0.5, more particularly between 80/20 and 98/2.
    [14" id="c-fr-0014]
    14. Use of a projectile according to one of the preceding claims for the protection of a parcel of trees against a pest insect characterized in that the projectile is projected and bursts on the trunk of the trees of the parcel to be protected; preferentially the projectile is projected with sufficient force to burst the envelope and to adhere all or part of the filling on the trunk.
    [15" id="c-fr-0015]
    15. Use according to claim 14, characterized in that the insect pest is selected from the group consisting of the butterfly of the pine processionary, the moth of the oak processionary, the boxworm, the bombyx and carpocapses.
    [16" id="c-fr-0016]
    16. Use according to claim 14, characterized in that the projectile is projected and bursts at the height of the canopy.
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    同族专利:
    公开号 | 公开日
    CN108135161A|2018-06-08|
    FR3041503B1|2017-10-20|
    CN108135161B|2021-02-19|
    EP3352568B1|2020-03-18|
    EP3352568A1|2018-08-01|
    AU2016325411A1|2018-05-17|
    CA2998906A1|2017-03-30|
    US10517292B2|2019-12-31|
    AU2016325411B2|2020-06-25|
    WO2017050956A1|2017-03-30|
    ES2795924T3|2020-11-25|
    US20180279607A1|2018-10-04|
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    法律状态:
    2016-09-12| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-31| EXTE| Extension to a french territory|Extension state: PF |
    2017-03-31| PLSC| Publication of the preliminary search report|Effective date: 20170331 |
    2017-09-07| PLFP| Fee payment|Year of fee payment: 3 |
    2018-01-19| GC| Lien (pledge) constituted|Effective date: 20171215 |
    2018-09-25| PLFP| Fee payment|Year of fee payment: 4 |
    2019-09-26| PLFP| Fee payment|Year of fee payment: 5 |
    2020-09-30| PLFP| Fee payment|Year of fee payment: 6 |
    2021-08-10| PLFP| Fee payment|Year of fee payment: 7 |
    2021-12-10| RG| Lien (pledge) cancelled|Effective date: 20211104 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1559087A|FR3041503B1|2015-09-25|2015-09-25|OXODEGRADABLE PROJECTILES CONTAINING PHEROMONES|FR1559087A| FR3041503B1|2015-09-25|2015-09-25|OXODEGRADABLE PROJECTILES CONTAINING PHEROMONES|
    AU2016325411A| AU2016325411B2|2015-09-25|2016-09-23|Oxo-degradable projectiles containing pheromones|
    US15/762,629| US10517292B2|2015-09-25|2016-09-23|Oxo-degradable projectiles containing pheromones|
    CN201680055941.2A| CN108135161B|2015-09-25|2016-09-23|Oxidizable and degradable projectile containing pheromones|
    CA2998906A| CA2998906A1|2015-09-25|2016-09-23|Oxo-degradable projectiles containing pheromones|
    EP16777594.9A| EP3352568B1|2015-09-25|2016-09-23|Oxo-degradable projectiles containing pheromones|
    PCT/EP2016/072668| WO2017050956A1|2015-09-25|2016-09-23|Oxo-degradable projectiles containing pheromones|
    ES16777594T| ES2795924T3|2015-09-25|2016-09-23|Oxodegradable projectiles containing pheromones|
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