WO2022058689A1 - Surface-coating fluid composition for absorbing and diffusing volatile compounds - Google Patents

Surface-coating fluid composition for absorbing and diffusing volatile compounds Download PDF

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Publication number
WO2022058689A1
WO2022058689A1 PCT/FR2021/051588 FR2021051588W WO2022058689A1 WO 2022058689 A1 WO2022058689 A1 WO 2022058689A1 FR 2021051588 W FR2021051588 W FR 2021051588W WO 2022058689 A1 WO2022058689 A1 WO 2022058689A1
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composition
copolymer
semiochemical
solid composition
block
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PCT/FR2021/051588
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French (fr)
Inventor
Yannick ESCUDIE
Patrick Durand
Olivier Guerret
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Melchior Material And Life Science France
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Publication of WO2022058689A1 publication Critical patent/WO2022058689A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/141—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers
    • A61K9/146—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers with organic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • Semiochemicals are volatile substances that are increasingly used in many fields, for example to control animal behavior or to regulate populations of insect pests.
  • these semiochemicals are molecules that are chemically sensitive and more particularly sensitive to oxidation (especially in the presence of UV or free radicals) or to temperatures because they have unsaturated chemical bonds (double or triple bonds), alcohol groups or strained ether cycles.
  • oxidation especially in the presence of UV or free radicals
  • temperatures because they have unsaturated chemical bonds (double or triple bonds), alcohol groups or strained ether cycles.
  • impurities by oxidation processes can have catastrophic effects on the effectiveness of semiochemicals (an attractant can for example become a repellent or the pheromone of a particular insect can be transformed into the pheromone of another insect).
  • liquid or fluid compositions of the paint type, comprising an active compound such as an insecticide for example, intended to be applied to supports, such as walls for example, in order to allow the diffusion of said compound in the air. ambient.
  • thermoplastic matrix for releasing semiochemicals was the subject of a patent application in 1996 (US005504142).
  • the matrix is a PEBAX® type copolymer.
  • Pebax® is a plasticizer-free flexible thermoplastic elastomer or polyamide composed of a regular linear chain of rigid polyamide segments and flexible polyether segments.
  • this type of matrix may require the use of a solvent serving as a vector for the active substance to penetrate into the copolymer matrix. These solvents necessary for the implementation of the process described in this invention are potentially harmful for the environment or can have a negative interaction with animals.
  • ethylene and vinyl acetate copolymer matrices have also been tested to deliver bioactive compounds such as food attractants, pesticides, as described in patent US5135744.
  • the mixing of the copolymer and the bioactive compound and the final shaping (extrusion) must be done at high temperatures (between 80 and 110°C) which is not feasible with most semiochemicals which are not do not support these transformation conditions or evaporate quickly at the outlet of the extruder, which makes the load of semiochemical substance in the plastic difficult to control.
  • patent WO2013156249A1 describes a composition comprising a pesticide and a random copolymer which contains, in polymerized form, acrylic or methacrylic acid (monomer A), a monopoly(C2-6 alkylene alcohol)(meth)acrylate terminated by a C12-C22 alkyl (monomer B), and a C1-C6 alkyl methacrylate (monomer C).
  • this type of random copolymer is obtained once again by polymerization with a radical generator (in the examples of this patent tert.-butylperpivalate) which, as already underlined, represents a danger of deterioration of the current semiochemical substances.
  • document EP0338732 describes a matrix for the release and diffusion of active substances such as perfumes and pheromones into the atmosphere.
  • the matrix is permeable to the active substances and is formed of a copolymer which can be sufficiently softened at a temperature between 45°C and 160°C to incorporate the substances therein.
  • the matrix is formed from a substantially linear block copolymer which is a reaction product of a polydiorganosiloxane which forms soft segments in said reaction product and a diisocyanate which forms hard segments, said soft segments comprising from 70 to 99% by weight, based on the weight of said copolymer.
  • the problem with such a matrix is that its manufacture involves high temperatures which are not compatible with certain pheromones. Furthermore, once the pheromone has been released, it is not possible to recharge the matrix.
  • WO0150859 also describes a slow release insect repellent composition
  • a slow release insect repellent composition comprising an insect repellent, an oleophilic chemical soluble in the insect repellent and a polysaccharide matrix in which the combination of the insect repellent and the oleophilic chemical is entrapped in the matrix of such so that the repellent is released from the matrix, a fabric substrate containing the composition, and a method of preparing the composition.
  • the problem with this type of composition is that the solidification goes through a drying step at temperatures that are incompatible with pheromone-type compounds which are very sensitive to heat and which will evaporate during this step. Also, as noted for other carriers, once the insect repellent compound has fully diffused, the composition cannot be refilled.
  • FR3032972 describes a composition comprising a polymer elastomer phase in the form of an acrylic block copolymer and an odorous active compound, methods for absorbing the odorous active compound and for releasing said odorous active compound for a given period of time.
  • This document also describes objects or articles comprising a polymeric elastomeric phase in the form of an acrylic block copolymer and an odorous active compound.
  • this document does not describe liquid or fluid compositions but compositions obtained by injection molding, extrusion, co-extrusion or extrusion/blow molding leading to the preparation of parts or profiled elements, blocks, tubes, sheets or films.
  • the present invention therefore proposes a new type of liquid composition, of the paint or ink type, which is applied to any support and forms a solid surface coating - or at the very least cohesive - and which can be loaded with a semiochemical compound then which can gradually release said compound over long periods of time.
  • the coating can be recharged with the semiochemical substance by simply bringing said substance into contact with the coating. This makes it possible to achieve the objective of adsorption, protection, controlled release, and this repeatedly, of said semiochemical substance over long periods of time.
  • the present invention aims, firstly, at a method for the diffusion of a semiochemical substance comprising the following steps:
  • the method according to the invention is characterized in that the solid composition comprising a polymeric resin further comprises at least one copolymer with acrylic blocks, said copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkylacrylate block; said copolymer being dispersed and immobilized in the polymeric resin.
  • the alkyl is a C1-C10, in particular C1-C8, linear or branched alkyl.
  • step a) is preceded by steps a1) to a3); step a1) comprising providing a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler and optionally at least one acrylic block copolymer, said block copolymer acrylics comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block; step a2) comprising the application of the liquid composition to a support and step a3) comprising the evaporation of the solvent.
  • the alkyl is a C1-C10, in particular C1-C8, linear or branched alkyl.
  • solid composition By the expression “solid composition” is meant here, as opposed to a “liquid composition”, a composition which does not flow under the effect of its own weight and is not deformable by the effect of its own weight. ; a solid composition can thus be semi-rigid or flexible.
  • a “liquid composition” (or fluid) is a composition that can flow under its own weight, be poured, decanted.
  • a liquid (or fluid) composition corresponds, in the context of the present invention, to a composition of paint or ink type, for example.
  • a “filler” is an ingredient that is inert with respect to semiochemical compounds, in general it is a mineral substance of white or slightly colored natural origin in the form of very fine particles, particles which are practically insoluble in the middle of the composition.
  • the filler is used, for example, to thicken the composition, to improve its grip, to give an aesthetic appearance or even to limit shrinkage once the solvent has evaporated and the composition has solidified.
  • the filler can be chosen from the group consisting of talc, carbonates, clays, as well as mixtures thereof.
  • polymeric resin resins usually used in compositions of the screen printing ink type, for example, and can include cellulosic resins, vinyl resins or even polyurethane resins, mono or bi-component.
  • the cellulosic resins typically comprise nitrocellulose resins of ethylcellulose, acetobutyrate or cellulose acetopropionate and can be combined with other resins of the alkyd, polyester, polyurethane or polyamides.
  • Vinyl resins typically include polyvinyl acetates, polyvinyl chlorides, vinyl acetate/vinyl chloride copolymers or polyvinyl ethers.
  • a thin layer in the context of the present invention, means a layer whose thickness is between 5 and 500 ⁇ m, in particular 10 and 400 ⁇ m, or even 20 and 300 ⁇ m, or even between 50 and 250 pm. This thickness may vary depending on the viscosity and the composition of the composition, the nature of the support and the number of applications on said support.
  • the method according to the invention is also characterized in that the solid composition is integral with a support, in particular in the form of a thin layer which adheres to said support on which it has been applied and has hardened.
  • the support is made of a material chosen from the group comprising glass, textile, paper, cardboard, plastic, brick, wood, leather, plant fibres, metal and ceramic.
  • support is meant here any material element which is totally or partially coated with the solid composition according to the invention.
  • a support can comprise or consist of a more or less extensive and more or less flat continuous surface such as a wall, opaque or transparent, for example a wall, a floor or a glazed expanse such as a window.
  • a support can also comprise an article, that is to say a discrete or individualized object, the surface of which will be coated, in whole or in part, with the solid composition according to the invention.
  • the invention thus relates to an article comprising a solid composition according to the invention.
  • the article according to the invention can be made of glass, textile, paper, cardboard, plastic, brick, wood, leather, plant fibers, metal or ceramic.
  • An article according to the invention is in the form of a post, guardian, fence, palisade, staple, hook, cardboard plate, glass plate, plastic plate, metal plate, cloth, tarpaulin, t-shirt for example .
  • the method according to the invention is characterized in that the copolymer with acrylic blocks is a bi-block copolymer or a tri-block copolymer.
  • the tri-block copolymer comprises at most 2 identical blocks.
  • the polyalkyl methacrylate is polymethyl methacrylate (PMMA).
  • the polyalkyl acrylate is chosen from the group consisting of polybutyl acrylate (PABu) and a copolymer of butyl acrylate and 2-ethylhexyl acrylate.
  • PABu polybutyl acrylate
  • the copolymer with acrylic blocks is a tri-block copolymer of the PMMA-PABu-PMMA type.
  • block polymer represents a polymer whose macromolecules consist of linearly linked blocks.
  • the blocks can be assembled directly or through a constituent unit which is not an integral part of the blocks.
  • block copolymer represents a block copolymer resulting from several species of polymers.
  • block represents the part of a macromolecule comprising a plurality of constituent units and which has at least one peculiarity of constitution or configuration which does not appear in the adjacent parts.
  • composition comprising a semiochemical substance refers to a composition, typically a liquid composition which comprises, or consists of, one or more semiochemical substances, optionally dissolved in a solvent.
  • Semiochemicals are categorized into pheromones - which enable communication between individuals of the same species - and allomones, kairomones and synomones which are exchanged between animals or plants belonging to different species. Semiochemicals can be perceived by different organs for volatile compounds, or for non-volatile compounds. The information carried by the semiochemicals can allow the location and recognition of a sexual partner, for example.
  • Semiochemicals and more particularly pheromones are chemical compounds of which a large number of examples (8000) are given in the database accessible online Pherobase (www.pherobase.com).
  • the semiochemical substance is a volatile semiochemical substance, in particular a volatile semiochemical substance with a fatty chain, and is advantageously chosen from the group of pheromones, in particular insect pheromones.
  • the volatile semiochemical substance is lipophilic and is a fatty chain pheromone.
  • fatty chain it is understood within the meaning of the present invention, a linear or branched hydrocarbon aliphatic chain, optionally unsaturated, comprising 5 to 18, 6 to 16 or 5 to 16 carbon atoms, thus conferring a character lipophilic to the semiochemical substance.
  • volatile refers to the ability of the semiochemical substance to change from the liquid state to the gaseous state, under certain conditions, that is to say at approximately 20°C and 760 mm Hg
  • a “volatile” liquid being a liquid whose saturation vapor pressure at 20° C. is greater than 0.01 mm Hg, preferably it is between 0.01 and 20, more preferably between 0.01 and 10 , more preferably between 0.01 and 5.
  • known pheromones that can be used according to the present invention are: volatile alkanols and alkenols having from 5 to 18 carbons, volatile alkanals and alkenals having from 5 to 18 carbons, alkanones having from 6 to 18 carbons, l,7-dioxaspirononane, 3-or 4-hydroxy-l,7-dioxaspiro-undecane, benzyl alcohol, Z-(9)-tricosene (muscature), heneicosene, diacetyl or alkanoic acids having 5 to 16 carbons such as caprylic acid, laurylic acid, pinene, methyl eugenol, ethyldodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane- carboxylate, mycrenone, cucurbitacin, trimedlure and (
  • the volatile semiochemical substance can be chosen from ferruginol, ferruginone or a ferruginol-ferruginone mixture.
  • fatty chain pheromones are: Z-5-Decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E -8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9 ,11-dodecadienyl acetate, Z-11-tridecenyl acetate, El 1-tridecenyl I acetate, tetradecenyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetete
  • the semiochemical substance is chosen from the group of pheromones, in particular from insect sex pheromones, in particular fatty chain insect sex pheromones, and more particularly still from the group consisting by pine processducy moth pheromones, oak processducy moth pheromones, boxwood moth pheromones, moth pheromones, codling moth pheromones, peach fly pheromones, sesame pheromones maize, eudemis pheromones, batrachedra pheromones, cocoa mirid pheromones, palm or banana weevil pheromones, eudemis pheromones and vine cochylis pheromones as well as than their mixtures.
  • the semiochemical substance in particular volatile, in particular still with a fatty chain, may be an insect sex pheromone.
  • the method according to the invention is characterized in that step d.) of diffusion of said semiochemical substance from the impregnated solid composition is carried out in the place of provision, in particular an agricultural plot, and that the method makes it possible to protect said plot against insect pests.
  • the solid composition is integral with a support to facilitate the provision in a parcel.
  • This provision may be temporary or for a longer period.
  • a support comprises an article which can be chosen from the group comprising a stake, a stake, a fence, a palisade, staple, hook, a plate, for example, which can be fixed in one or more points of the parcel, and remaining there for the season or even longer.
  • Such articles and supports can be coated with the solid composition according to the invention and serve as a diffuser for the semiochemical compound within the plot. These items may be recovered for reloading or recycling or storage at the end of the season.
  • a support comprises an article which can be chosen from the group comprising cardboard plate, glass plate, plastic plate, metal plate, cloth, tarpaulin, t-shirt or fabric, for example.
  • a support for example an article in the form of cardboard or plate, coated with the solid composition according to the invention can be placed at regular intervals within the parcel and carry out the diffusion; and can be recovered for reloading or recycling or storage at the end of the season.
  • the pheromones according to the invention are natural or synthetic pheromones.
  • the semiochemical substance may be protected against the action of light and/or that of oxygen. Indeed, when the diffuser articles according to the invention are used in cultures for several months, it may be preferable to protect the semiochemical substance from an alteration over time.
  • Those skilled in the art are accustomed to adding antioxidants and anti-UV to semiochemical substances to fulfill this function.
  • An advantage of the process according to the invention is that the UV stabilizers or the antioxidants can already be contained in the liquid composition before its application to a support or its impregnation with the semiochemical compound or else added to the composition comprising the semiochemical substance before that -it is incorporated / adsorbed in / by the polymeric composition. These two methods ensure intimate protection of the semiochemical until it is released into the external environment.
  • the antioxidants can be chosen from the group consisting of vitamin E, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) used alone or as a mixture. These antioxidants protect the semiochemical from degradation and can be added in amounts, in percentage by weight of the liquid or solid composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5 and 2%.
  • the anti-UV additives can be chosen from the group consisting of beta-carotene, p-aminobenzoic acid, hindered amines and hindered alkoxyamines used alone or as a mixture. These UV stabilizers protect the semiochemicals from degradation by light and can be added in quantities, as a percentage by weight of the composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5 and 2%.
  • the present invention also relates to a liquid composition
  • a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, optionally at least one semiochemical substance and at least one copolymer with acrylic blocks, said copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block.
  • Such a liquid composition is thus in the form of a composition of the paint or ink type for surface coating which allows the coating of a support.
  • liquid composition is applied to a solid support which will be partially or totally coated with the liquid composition which will be solidified following the evaporation of the solvent and will form the solid composition.
  • composition according to the invention is in fact that it can be applied to any form of object.
  • liquid (or fluid) nature makes it possible to apply it to any surface and to cover all or part of a given support.
  • a solid or flexible support such as a collar, a fabric, a stake, a bar, a plate or a plate in any material for example, and this in relation to the mode of use. and the intended venue.
  • the application can be carried out with a roller, a brush, by spraying, by dipping or by any other suitable means making it possible to coat the support in whole or in part with the fluid composition.
  • the ease of application of the liquid composition according to the invention also makes it possible to use it as a paint or an ink and to carry out any application on any support, in particular textiles, to cover it in whole or in part by defining logos or registrations and this according to the will or the desire of the user.
  • liquid composition according to the invention can be used in a method of printing by screen printing techniques known to those skilled in the art and this for screen printing any support of their choice and this whatever the material, for example on textile to obtain coated articles such as clothes, toys or any utensil for example.
  • the liquid composition then solidifies via the evaporation of the solvent, which makes it possible to obtain a solid composition in the form of a surface coating comprising, or consisting of, a continuous phase of polymeric resin in which the optional pigment is dispersed, the optional filler, the at least one optional acrylic block copolymer, said acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, as well as the optional semiochemical substance.
  • the liquid composition according to the invention is also characterized in that the semiochemical substance represents between 0% and 80% by weight of the liquid composition, particularly between 1 and 60%, more particularly still between 5 and 50%.
  • the supports such as articles as mentioned above, coated with the solid composition according to the invention, if it does not already contain the semiochemical compound, can then be impregnated and loaded with a composition comprising a semiochemical substance.
  • This impregnation, or loading can be carried out by simply bringing the solid composition according to the invention into contact with a composition comprising a semiochemical compound.
  • the composition comprising said semiochemical compound is in the form of a liquid composition comprising said semiochemical compound and which is brought into contact with the solid composition.
  • Such bringing into contact can be carried out by vaporization of a liquid composition comprising the semiochemical compound, but also by painting with a brush or a roller or by dipping, for example.
  • composition according to the invention can be charged or re-charged with a semiochemical substance, such as a pheromone.
  • a wall covered with the solid composition according to the invention may be reimpregnated with a composition comprising a semiochemical substance by bringing it into contact as explained further on, for example by vaporization.
  • a solid composition comprising a polymeric resin constituting a continuous phase in which is dispersed and immobilized at least one acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, an optional filler and a optional pigment;
  • the solid composition according to the invention is also characterized in that once impregnated with the semiochemical substance, the latter represents between 1% and 80% by weight of the solid composition, particularly between 1 and 50%, between 5 and 50% , more particularly between 5 and 40%, or even between 5 and 30%, or even between 5 and 20%.
  • a solid composition according to the invention can thus diffuse and gradually release the semiochemical substance into the environment until the quantity of semiochemical substance contained is exhausted. It can then be reused for reloading as described above, then a new broadcast. And this can be repeated several times.
  • copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block is found dispersed within the continuous resin phase in the form of inclusions which will contribute to capturing, absorbing, retaining and release the semiochemical.
  • the invention thus relates to a solid composition according to the invention, characterized in that the polymeric resin constitutes a continuous phase in which is dispersed and immobilized the at least one copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least a polyalkylacrylate block, the optional filler and the optional pigment.
  • the invention finally relates to the use of a solid or liquid composition according to the invention comprising at least one semiochemical substance for the diffusion of said semiochemical substance.
  • the invention finally relates to the use of a solid or liquid composition according to the invention for the absorption and diffusion of a semiochemical substance.
  • Block copolymer materials are materials from the nanostrenth® range sold by Arkema, such as M53, M65 or M53F, for example.
  • the pheromones are synthesized by M2i Development or M2i Salin according to methods already reported in the literature.
  • the pheromone of Lobesia Botrana (Eudemis de la vigne) is 7E,9Z-dodecadienylacetate (CAS: 54364-62-4) with a molar mass of 224.34 g/mol.
  • Methyl laurate (CAS 111-82-0) with a molar mass of 214.34 g/mol is one of the components of the soothing pheromone composition of ADAPTIL®.
  • Commercial inks are purchased from TIFLEX.
  • Example 1 Demonstration of the retention effect on films of block copolymers: A solution of block copolymer M53 in ethyl acetate is prepared at 20% by weight. Using a glass pipette, lOmL of solution is placed in an aluminum tray 10 cm in diameter. The tray is placed in a ventilated oven for 24 h. A homogeneous film of block copolymer is obtained. 10 trays are thus prepared and numbered from 1 to 20.
  • lobesia pheromone (7E,9Z-dodecadienylacetate) On those numbered from 6 to 10, are deposited 100 mg of methyl laurate.
  • the two active ingredients are applied to the film using a spray of pheromone solution diluted to 20% in pentane.
  • the trays are left in the open air until the visual disappearance of the active ingredient.
  • the trays are placed in a ventilated oven maintained at 40°C (lobesia) or 30°C (methyl laurate). Two blank trays are loaded with the same amount of each active.
  • the trays are regularly analyzed to determine the level of residual pheromone (by simple weighing or preferably by gas chromatography).
  • Table 1 below shows the diffusion time in the oven necessary to reach below 10% of residual active ingredient with respect to the quantity introduced.
  • This example shows the retention effect of a surface treated with a deposition of fi m of block copolymers compared with an untreated surface.
  • Example 2 Demonstration of the effect of the copobloc by comparison of an ink not containing additives of block copolymers with an ink containing additives.
  • Square glass plates with a side of 10 cm are printed by traditional screen printing with two commercial inks of the polyworks (TIFLEX) and vinyl (TIFLEX) type, blue in color.
  • a series of plates is used without treatment while the other series is treated by spraying a 10% solution of M53 block copolymers. Once dried, these plates show no visual difference with the untreated plates.
  • the four series of plates are sprayed with lobesia pheromone and methyl laurate in a 20% solution in pentane.
  • the plates are left in the air and then placed in a ventilated oven at 30° C. and 40° C. respectively for the plates impregnated with lobesia pheromone and the plates impregnated with methyl laurate.
  • the trays are regularly analyzed to determine the level of residual pheromone (by simple weighing or preferably by gas chromatography).
  • Table 2 below shows the diffusion time in the oven necessary to reach below 10% of residual active ingredient with respect to the quantity introduced.

Abstract

The invention relates to a paint- or ink-type liquid composition that is applied to any substrate, forms a solid surface coating, can be loaded with a semiochemical compound and is capable of gradually diffusing said compound over long periods.

Description

DESCRIPTION DESCRIPTION
TITRE : COMPOSITION FLUIDE POUR REVETEMENT DE SURFACE POUR ABSORPTION ET DIFFUSION DE COMPOSES VOLATILS TITLE: FLUID COMPOSITION FOR SURFACE COATING FOR ABSORPTION AND DIFFUSION OF VOLATILE COMPOUNDS
Les substances sémiochimiques (pheromones, kairomones, allomones et synomones), sont des substances volatiles de plus en plus utilisées dans de nombreux domaines que ce soit, par exemple, pour contrôler le comportement des animaux ou pour réguler les populations d'insectes ravageurs. Semiochemicals (pheromones, kairomones, allomones and synomones) are volatile substances that are increasingly used in many fields, for example to control animal behavior or to regulate populations of insect pests.
Par ailleurs, ces substances sémiochimiques sont des molécules sensibles chimiquement et plus particulièrement sensibles à l'oxydation (notamment en présence d'UV ou de radicaux libres) ou aux températures car présentant des liaisons chimiques insaturées (double ou triple liaisons), des groupes alcool ou des cycles éther tendus. Or la formation d'impuretés par des processus d'oxydation peut avoir des effets catastrophiques sur l'efficacité des sémiochimiques (un attractant peut par exemple devenir un répulsif ou bien la phéromone d'un insecte en particulier peut se transformer en la phéromone d'un autre insecte). Furthermore, these semiochemicals are molecules that are chemically sensitive and more particularly sensitive to oxidation (especially in the presence of UV or free radicals) or to temperatures because they have unsaturated chemical bonds (double or triple bonds), alcohol groups or strained ether cycles. However, the formation of impurities by oxidation processes can have catastrophic effects on the effectiveness of semiochemicals (an attractant can for example become a repellent or the pheromone of a particular insect can be transformed into the pheromone of another insect).
Un des problèmes majeurs qui se pose pour pouvoir utiliser de manière optimale ces substances sémiochimiques est la possibilité de les stocker et de les relarguer à l'aide de matériaux permettant non seulement la préservation de la pureté des sémiochimiques pendant la fabrication du dispositif et pendant le temps d'utilisation, mais aussi un relargage contrôlé à des taux suffisants sur de longues périodes. Un autre problème est de pouvoir charger plusieurs fois les matériaux afin d'éviter de devoir fabriquer et utiliser un nouvel article à chaque nouvelle utilisation souhaitée. One of the major problems that arises in order to be able to use these semiochemicals in an optimal manner is the possibility of storing them and releasing them using materials that not only allow the preservation of the purity of the semiochemicals during the manufacture of the device and during the time of use, but also controlled release at sufficient rates over long periods. Another issue is being able to load materials multiple times to avoid having to craft and use a new item each time you want to use it again.
Il existe des compositions liquides ou fluides, de type peintures, comprenant un composé actif tel qu'un insecticide par exemple, destinées à être appliquées sur des supports, tel que des murs par exemple, afin de permettre la diffusion dudit composé dans l'air ambiant. There are liquid or fluid compositions, of the paint type, comprising an active compound such as an insecticide for example, intended to be applied to supports, such as walls for example, in order to allow the diffusion of said compound in the air. ambient.
Cependant, une fois la diffusion terminée par épuisement du composé contenu dans le revêtement, il n'est plus possible de reproduire la diffusion sauf à répéter l'application d'une nouvelle couche de composition, c'est à dire à remettre une couche de peinture contenant le compose actif à diffuser. Cela est lourd et revient cher car implique des applications répétitives de la composition de type peinture et une superposition de couches sur le support, ce qui n'est pas souhaitable sur le long terme. However, once the diffusion is complete by exhaustion of the compound contained in the coating, it is no longer possible to reproduce the diffusion except to repeat the application of a new layer of composition, i.e. to reapply a layer of paint containing the active compound to be diffused. This is cumbersome and expensive because it involves repetitive applications of the paint-type composition and superimposition of layers on the support, which is not desirable in the long term.
L'utilisation de matrices polymériques pour le relargage de substances actives, notamment des substances sémiochimiques est connue depuis longtemps puisque déjà évoquée par exemple dans la revue de Campion (D.G. Campion, Pestic. Sci. 1978, 9, 434-440). Il est notamment fait référence dans cette publication à l'utilisation de matrices caoutchouteuses (ou élastomériques). Cependant, il y est aussi souligné que de telles matrices ne permettent pas un relargage continu dans le temps et présentent une grande sensibilité aux conditions atmosphériques. The use of polymeric matrices for the release of active substances, in particular semiochemical substances, has been known for a long time since it has already been mentioned for example in the review by Campion (D.G. Campion, Pestic. Sci. 1978, 9, 434-440). In particular, reference is made in this publication to the use of rubbery (or elastomeric) matrices. However, it is also emphasized that such matrices do not allow continuous release over time and are highly sensitive to atmospheric conditions.
Plus tard, d'autres matrices élastomériques ont été proposées : par exemple, en 1987, dans le brevet US4703070. Mais, ces matrices élastomériques nécessitent d'incorporer la substance active avant que la matrice élastomérique ne soit totalement réticulée. Or, à cause de leurs structures chimiques spécifiques (liaison insaturées, présence de fonctions alcool...) peu de substances sémiochimiques peuvent supporter sans détérioration soit les hautes températures nécessaires à la fin de la réticulation, soit les composants réactifs du prépolymère. Or l'activité des substances sémiochimiques est fortement influencée par une détérioration même légère de la molécule (comme un changement d'isomérie par exemple).Later, other elastomeric matrices were proposed: for example, in 1987, in patent US4703070. However, these elastomeric matrices require the active substance to be incorporated before the elastomeric matrix is completely crosslinked. However, because of their specific chemical structures (unsaturated bonds, presence of alcohol functions, etc.), few semiochemical substances can withstand without deterioration either the high temperatures necessary at the end of the crosslinking, or the reactive components of the prepolymer. However, the activity of semiochemicals is strongly influenced by even slight deterioration of the molecule (such as a change in isomerism, for example).
Une autre matrice thermoplastique pour le relargage de sémiochimiques a fait l'objet d'un dépôt de brevet en 1996 (US005504142). Dans ce cas, la matrice est un copolymère de type PEBAX®. Le Pebax® est un élastomère thermoplastique ou un polyamide flexible sans plastifiant composé d'une chaîne linéaire régulière de segments polyamides rigides et de segments polyéther flexibles. Cependant ce type de matrice peut nécessiter l'utilisation d'un solvant servant de vecteur à la substance active pour pénétrer dans la matrice copolymère. Ces solvants nécessaires à la mise en œuvre du procédé décrit dans cette invention sont potentiellement nocifs pour l'environnement ou peuvent avoir une interaction négative avec les animaux. La présence de tels solvants (dérivés de l'acide undécylénique aux propriétés biocides bien connues de l'homme du métier) est donc rédhibitoire pour une utilisation d'une telle matrice pour stocker et relarguer des substances sémiochimiques. Une autre grande famille de matrices copolymères a ensuite été proposée à base de polyéthylène glycol (PEG). En 2005 par exemple, Brown et al (J. Am. Chem. Soc. 2005, 127, 11238-11239), proposaient d'utiliser un copolymère à base de polyéthylène glycol (PEG) et d'un fluoropolymère hydrophobe hyperbranché pour stocker et relarguer un alcool terpénique insaturé (le géraniol). Bien que montrant de grandes capacités à stocker cette molécule, un tel copolymère conduisait à des temps de relargage de la substance active très réduits ce qui est incompatible avec les relargages sur des longues durées nécessaires dans l'utilisation des sémiochimiques dans l'agriculture. En 2010, Shakil et al (p228 de la revue de M. Kah dans Environment International 63 (2014) 224-235) proposaient des formulations aqueuses à base de copolymères amphiphiles contenant des blocs PEG pour relarguer des insecticides. Cependant ces formulations aqueuses présentent l'inconvénient de ne pas être solides et de la présence d'eau peut induire des modifications chimiques des sémiochimiques.Another thermoplastic matrix for releasing semiochemicals was the subject of a patent application in 1996 (US005504142). In this case, the matrix is a PEBAX® type copolymer. Pebax® is a plasticizer-free flexible thermoplastic elastomer or polyamide composed of a regular linear chain of rigid polyamide segments and flexible polyether segments. However, this type of matrix may require the use of a solvent serving as a vector for the active substance to penetrate into the copolymer matrix. These solvents necessary for the implementation of the process described in this invention are potentially harmful for the environment or can have a negative interaction with animals. The presence of such solvents (derivatives of undecylenic acid with biocidal properties well known to those skilled in the art) is therefore unacceptable for the use of such a matrix for storing and releasing semiochemical substances. Another large family of copolymer matrices was then proposed based on polyethylene glycol (PEG). In 2005, for example, Brown et al (J. Am. Chem. Soc. 2005, 127, 11238-11239), proposed using a copolymer based on polyethylene glycol (PEG) and a hyperbranched hydrophobic fluoropolymer to store and release an unsaturated terpene alcohol (geraniol). Although showing great capacities for storing this molecule, such a copolymer led to very short release times of the active substance, which is incompatible with the releases over long periods necessary in the use of semiochemicals in agriculture. In 2010, Shakil et al (p228 of M. Kah's review in Environment International 63 (2014) 224-235) proposed aqueous formulations based on amphiphilic copolymers containing PEG blocks to release insecticides. However, these aqueous formulations have the disadvantage of not being solid and the presence of water can induce chemical modifications of the semiochemicals.
Les matrices copolymères d'éthylène et de vinyl acétate ont aussi été testées pour délivrer des composés bioactifs tels que des attractants alimentaires, des pesticides, comme décrit dans le brevet US5135744. The ethylene and vinyl acetate copolymer matrices have also been tested to deliver bioactive compounds such as food attractants, pesticides, as described in patent US5135744.
Cependant, le mélange du copolymère et du composé bioactif et la mise en forme finale (extrusion) doivent se faire à des températures élevées (entre 80 et 110°C) ce qui n'est pas réalisable avec la plupart des substances sémiochimiques qui soit ne supportent pas ces conditions de transformation soit s'évaporent rapidement à la sortie de l'extrudeuse ce qui rend la charge de substance sémiochimique dans le plastique difficilement contrôlable. However, the mixing of the copolymer and the bioactive compound and the final shaping (extrusion) must be done at high temperatures (between 80 and 110°C) which is not feasible with most semiochemicals which are not do not support these transformation conditions or evaporate quickly at the outlet of the extruder, which makes the load of semiochemical substance in the plastic difficult to control.
D'autres copolymères ont aussi été proposés par exemple dans WO2012/095444, qui revendique la formation de microcapsules composées de plusieurs polymères dont des Cl- C24-a I kyl ester d'acide acrylique. Ce type de matrice ne peut être utilisé que pour des substances sémiochimiques ne présentant pas de sensibilité aux peroxydes qui sont nécessaires à la polymérisation de la matrice, c'est-à-dire pour un nombre restreint de substances sémiochimiques. De même, le brevet WO2013156249A1 décrit une composition comprenant un pesticide et un copolymère statistique qui contient sous forme polymérisée de l'acide acrylique ou méthacrylique (monomère A), un mono poly(C2-6 alkylène alcool)(méth)acrylate terminé par un alkyle C12-C22(monomère B), et un méthacrylate d' alkyle C1-C6 (monomère C). Cependant ce type de copolymère statistique est obtenu une fois encore par polymérisation avec un générateur de radical (dans les exemples de ce brevet du tert.-butylperpivalate) qui comme déjà souligné représente un danger de détérioration des substances sémiochimiques courantes. Par exemple, il est bien connu que la (E,Z)-7,9 dodécadiénylacétate (phéromone sexuelle de l'eudémis, tordeuse de la vigne) se transforme en (E,E)-7,9 dodécadiénylacétate qui n'a aucun effet sur l'insecte. Other copolymers have also been proposed, for example in WO2012/095444, which claims the formation of microcapsules composed of several polymers including Cl-C24-a I kyl ester of acrylic acid. This type of matrix can only be used for semiochemical substances not exhibiting sensitivity to the peroxides which are necessary for the polymerization of the matrix, that is to say for a limited number of semiochemical substances. Similarly, patent WO2013156249A1 describes a composition comprising a pesticide and a random copolymer which contains, in polymerized form, acrylic or methacrylic acid (monomer A), a monopoly(C2-6 alkylene alcohol)(meth)acrylate terminated by a C12-C22 alkyl (monomer B), and a C1-C6 alkyl methacrylate (monomer C). However, this type of random copolymer is obtained once again by polymerization with a radical generator (in the examples of this patent tert.-butylperpivalate) which, as already underlined, represents a danger of deterioration of the current semiochemical substances. For example, it is well known that (E,Z)-7,9 dodecadienylacetate (sex pheromone of eudemis, grape berry moth) converts to (E,E)-7,9 dodecadienylacetate which has no effect on the insect.
De même le document EP0338732 décrit une matrice pour le relargage et la diffusion de substances actives telles que des parfums et des phéromones dans l'atmosphère. La matrice est perméable aux substances actives et est formée d'un copolymère qui peut être suffisamment ramolli à une température comprise entre 45°C et 160°C pour y incorporer les substances. La matrice est formée d'un copolymère séquencé sensiblement linéaire qui est un produit de réaction d'un polydiorganosiloxane qui forme des segments mous dans ledit produit de réaction et un diisocyanate qui forme des segments durs, lesdits segments mous comprenant de 70 à 99 % en poids, sur la base du poids dudit copolymère. Le problème avec une telle matrice est que sa fabrication implique des températures élevées non compatibles avec certaines phéromones. En outre, une fois la phéromone diffusée, il n'est pas possible de recharger la matrice. Similarly, document EP0338732 describes a matrix for the release and diffusion of active substances such as perfumes and pheromones into the atmosphere. The matrix is permeable to the active substances and is formed of a copolymer which can be sufficiently softened at a temperature between 45°C and 160°C to incorporate the substances therein. The matrix is formed from a substantially linear block copolymer which is a reaction product of a polydiorganosiloxane which forms soft segments in said reaction product and a diisocyanate which forms hard segments, said soft segments comprising from 70 to 99% by weight, based on the weight of said copolymer. The problem with such a matrix is that its manufacture involves high temperatures which are not compatible with certain pheromones. Furthermore, once the pheromone has been released, it is not possible to recharge the matrix.
Le document W00150859 décrit aussi une composition insectifuge à libération lente comprenant un insectifuge, un produit chimique oléophile soluble dans l'insectifuge et une matrice de type polysaccharidique dans laquelle la combinaison de l'insectifuge et du produit chimique oléophile est piégée dans la matrice de telle sorte que le répulsif soit libéré de la matrice, un substrat de tissu contenant la composition et un procédé de préparation de la composition. Le problème avec ce type de composition est que la solidification passe par une étape de séchage à des températures incompatibles avec des composés de type phéromones qui sont très sensibles à la chaleur et qui vont s'évaporer lors de cette étape. De plus, comme indiqué pour d'autres supports, une fois le composé insectifuge complètement diffusé, la composition ne peut pas être rechargée. WO0150859 also describes a slow release insect repellent composition comprising an insect repellent, an oleophilic chemical soluble in the insect repellent and a polysaccharide matrix in which the combination of the insect repellent and the oleophilic chemical is entrapped in the matrix of such so that the repellent is released from the matrix, a fabric substrate containing the composition, and a method of preparing the composition. The problem with this type of composition is that the solidification goes through a drying step at temperatures that are incompatible with pheromone-type compounds which are very sensitive to heat and which will evaporate during this step. Also, as noted for other carriers, once the insect repellent compound has fully diffused, the composition cannot be refilled.
FR3032972 décrit une composition comprenant une phase élastomère polymère sous la forme d'un copolymère séquencé acrylique et un composé actif odorant, des méthodes d'absorption du composé actif odorant et de libération dudit composé actif odorant pendant une période de temps donnée. Ce document décrit aussi des objets ou des articles comprenant une phase élastomère polymère sous la forme d'un copolymère séquencé acrylique et un composé actif odorant. Ce document ne décrit cependant pas des compositions liquides ou fluides mais des compositions obtenues par moulage par injection, extrusion, co-extrusion ou moulage par extrusion/soufflage menant à la préparation de parties ou d'éléments profilés, de blocs, de tubes, de feuilles ou encore de films. FR3032972 describes a composition comprising a polymer elastomer phase in the form of an acrylic block copolymer and an odorous active compound, methods for absorbing the odorous active compound and for releasing said odorous active compound for a given period of time. This document also describes objects or articles comprising a polymeric elastomeric phase in the form of an acrylic block copolymer and an odorous active compound. However, this document does not describe liquid or fluid compositions but compositions obtained by injection molding, extrusion, co-extrusion or extrusion/blow molding leading to the preparation of parts or profiled elements, blocks, tubes, sheets or films.
La présente invention propose donc un nouveau type de composition liquide, de type peinture ou encre, qui est appliquée sur tout support et forme un revêtement de surface solide - ou à tout le moins cohésif - et qui peut être chargé par un composé sémiochimique puis qui peut diffuser progressivement ledit composé sur de longues périodes. En outre, une fois la diffusion dudit composé terminée, le revêtement peut être rechargé avec la substance sémiochimique par simple mise en contact de ladite substance avec le revêtement. Cela permet d'atteindre l'objectif d'adsorption, de protection, de relargage contrôlé, et ce de manière répétée, de ladite substance sémiochimique sur de longues durées. The present invention therefore proposes a new type of liquid composition, of the paint or ink type, which is applied to any support and forms a solid surface coating - or at the very least cohesive - and which can be loaded with a semiochemical compound then which can gradually release said compound over long periods of time. In addition, once the diffusion of said compound is complete, the coating can be recharged with the semiochemical substance by simply bringing said substance into contact with the coating. This makes it possible to achieve the objective of adsorption, protection, controlled release, and this repeatedly, of said semiochemical substance over long periods of time.
Ainsi la présente invention vise, en premier lieu, une méthode de diffusion d'une substance sémiochimique comprenant les étapes suivantes : Thus the present invention aims, firstly, at a method for the diffusion of a semiochemical substance comprising the following steps:
- a. fourniture d'une composition solide comprenant une résine polymérique, une charge optionnelle et un pigment optionnel, - at. supply of a solid composition comprising a polymeric resin, an optional filler and an optional pigment,
- b. Mise en contact d'une composition comprenant une substance sémiochimique avec la composition solide, - b. Bringing a composition comprising a semiochemical substance into contact with the solid composition,
- c. Imprégnation de la composition solide par la composition comprenant la substance sémiochimique, - vs. Impregnation of the solid composition with the composition comprising the semiochemical substance,
- d. Diffusion de ladite substance sémiochimique depuis la composition solide,-d. Diffusion of said semiochemical substance from the solid composition,
- e. optionnellement, répétition des étapes b à d. - e. optionally repeating steps b through d.
Selon un mode de réalisation, la méthode selon l'invention est caractérisée en ce que la composition solide comprenant une résine polymérique comprend en outre au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle ; le dit copolymère étant dispersé et immobilisé dans la résine polymérique. Typiquement l'alkyle est un alkyle en C1-C10, en particulier C1-C8, linéaire ou branché.According to one embodiment, the method according to the invention is characterized in that the solid composition comprising a polymeric resin further comprises at least one copolymer with acrylic blocks, said copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkylacrylate block; said copolymer being dispersed and immobilized in the polymeric resin. Typically the alkyl is a C1-C10, in particular C1-C8, linear or branched alkyl.
Selon un mode de réalisation particulier, la méthode selon l'invention est caractérisée en ce que l'étape a) est précédée des étapes al) à a3) ; l'étape al) comprenant la fourniture d'une composition liquide comprenant au moins une résine polymérique, au moins un solvant, optionnellement au moins un pigment, optionnellement au moins une charge et optionnellement au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle ; l'étape a2) comprenant l'application de la composition liquide sur un support et l'étape a3) comprenant l'évaporation du solvant. Typiquement l'alkyle est un alkyle en C1-C10, en particulier C1-C8, linéaire ou branché. According to a particular embodiment, the method according to the invention is characterized in that step a) is preceded by steps a1) to a3); step a1) comprising providing a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler and optionally at least one acrylic block copolymer, said block copolymer acrylics comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block; step a2) comprising the application of the liquid composition to a support and step a3) comprising the evaporation of the solvent. Typically the alkyl is a C1-C10, in particular C1-C8, linear or branched alkyl.
Par l'expression « composition solide », on entend ici, par opposition à une « composition liquide », une composition qui ne coule pas sous l'effet de son propre poids et n'est pas déformable par l'effet de son propre poids ; une composition solide peut être ainsi semi- rigide ou souple. A contrario, une « composition liquide » (ou fluide) est une composition pouvant s'écouler sous son propre poids, être versée, transvasée. Une composition liquide (ou fluide) correspond, dans le cadre de la présente invention à une composition de type peinture ou encre, par exemple. By the expression "solid composition" is meant here, as opposed to a "liquid composition", a composition which does not flow under the effect of its own weight and is not deformable by the effect of its own weight. ; a solid composition can thus be semi-rigid or flexible. Conversely, a “liquid composition” (or fluid) is a composition that can flow under its own weight, be poured, decanted. A liquid (or fluid) composition corresponds, in the context of the present invention, to a composition of paint or ink type, for example.
Une « charge » est un ingrédient inerte vis-à-vis des composés sémiochimiques, en général il s'agit d'une substance minérale d'origine naturelle blanche ou légèrement colorée sous forme de particules très fines, particules qui sont pratiquement insolubles dans le milieu de la composition. La charge sert par exemple à épaissir la composition, à améliorer son accroche, donner un aspect esthétique ou encore limiter le retrait un fois le solvant évaporé et la composition solidifiée. La charge peut être choisie dans le groupe constitué par le talc, les carbonates, les argiles, ainsi que leurs mélanges. A "filler" is an ingredient that is inert with respect to semiochemical compounds, in general it is a mineral substance of white or slightly colored natural origin in the form of very fine particles, particles which are practically insoluble in the middle of the composition. The filler is used, for example, to thicken the composition, to improve its grip, to give an aesthetic appearance or even to limit shrinkage once the solvent has evaporated and the composition has solidified. The filler can be chosen from the group consisting of talc, carbonates, clays, as well as mixtures thereof.
Par résine polymérique on entend ici des résines usuellement utilisées dans les compositions de type encre de sérigraphie par exemple et peut comprendre les résines cellulosiques, les résines vinyliques ou encore les résines polyuréthanes, mono ou bicomposants. Les résines cellulosiques comprennent typiquement des résines nitrocellulosiques d'éthylcell ulose, d'acetobutyrate ou acétopropionate de cellulose et peuvent être associées à d'autres résines de type alkydes, polyesters, polyuréthane ou polyamides. Les résines vinyliques comprennent typiquement des acétates de polyvinyle, des polychlorures de vinyle, des copolymères d'acétate de vinyle/chlorure de vinyle ou des éthers polyvinyliques. By polymeric resin is meant here resins usually used in compositions of the screen printing ink type, for example, and can include cellulosic resins, vinyl resins or even polyurethane resins, mono or bi-component. The cellulosic resins typically comprise nitrocellulose resins of ethylcellulose, acetobutyrate or cellulose acetopropionate and can be combined with other resins of the alkyd, polyester, polyurethane or polyamides. Vinyl resins typically include polyvinyl acetates, polyvinyl chlorides, vinyl acetate/vinyl chloride copolymers or polyvinyl ethers.
Une couche mince, dans le cadre de la présente invention, s'entend d'une couche dont l'épaisseur est comprise entre de 5 et 500pm, en particulier de 10 et 400 pm, voire de 20 et 300 pm, voire encore entre 50 et 250 pm. Cette épaisseur pourra varier en fonction de la viscosité et de la composition de la composition, de la nature du support ainsi que du nombre d'applications sur ledit support. A thin layer, in the context of the present invention, means a layer whose thickness is between 5 and 500 μm, in particular 10 and 400 μm, or even 20 and 300 μm, or even between 50 and 250 pm. This thickness may vary depending on the viscosity and the composition of the composition, the nature of the support and the number of applications on said support.
La méthode selon l'invention est aussi caractérisée en ce que la composition solide est solidaire d'un support, en particulier sous la forme d'une couche mince qui adhère audit support sur lequel elle a été appliquée et a durci. The method according to the invention is also characterized in that the solid composition is integral with a support, in particular in the form of a thin layer which adheres to said support on which it has been applied and has hardened.
Selon un mode de réalisation particulier, le support est en une matière choisie dans le groupe comprenant verre, textile, papier, carton, plastique, brique, bois, cuir, fibres végétales, métal et céramique. According to a particular embodiment, the support is made of a material chosen from the group comprising glass, textile, paper, cardboard, plastic, brick, wood, leather, plant fibres, metal and ceramic.
Par l'expression support, on entend ici tout élément matériel qui est revêtu en totalité ou partiellement par la composition solide selon l'invention. By the expression support is meant here any material element which is totally or partially coated with the solid composition according to the invention.
Un support peut comprendre ou consister en une surface continue plus ou moins étendue et plus ou moins plane comme une paroi, opaque ou transparente, par exemple un mur, un sol ou une étendue vitrée telle qu'une fenêtre. A support can comprise or consist of a more or less extensive and more or less flat continuous surface such as a wall, opaque or transparent, for example a wall, a floor or a glazed expanse such as a window.
Un support peut aussi comprendre un article, c'est-à-dire un objet discret ou individualisé, dont la surface sera revêtue, en totalité ou en partie, par la composition solide selon l'invention. A support can also comprise an article, that is to say a discrete or individualized object, the surface of which will be coated, in whole or in part, with the solid composition according to the invention.
L'invention vise ainsi un article comprenant une composition solide selon l'invention.The invention thus relates to an article comprising a solid composition according to the invention.
L'article selon l'invention peut être en verre, textile, papier, carton, plastique, brique, bois, cuir, fibres végétales, métal ou céramique. Un article selon l'invention se présente sous la forme d'un piquet, tuteur, clôture, palissade, agrafe, crochet, plaque en carton, plaque en verre, plaque en plastique, plaque métallique, chiffon, bâche, t-shirt par exemple. Selon un mode avantageux de réalisation, lorsque la composition solide comprenant une résine polymérique comprend en outre au moins un copolymère à blocs acryliques, la méthode selon l'invention est caractérisée en ce que le copolymère à blocs acryliques est un copolymère bi-blocs ou un copolymère tri-blocs. The article according to the invention can be made of glass, textile, paper, cardboard, plastic, brick, wood, leather, plant fibers, metal or ceramic. An article according to the invention is in the form of a post, guardian, fence, palisade, staple, hook, cardboard plate, glass plate, plastic plate, metal plate, cloth, tarpaulin, t-shirt for example . According to an advantageous embodiment, when the solid composition comprising a polymeric resin also comprises at least one copolymer with acrylic blocks, the method according to the invention is characterized in that the copolymer with acrylic blocks is a bi-block copolymer or a tri-block copolymer.
Plus particulièrement, le copolymère tri-blocs comprend au plus 2 blocs identiques. More particularly, the tri-block copolymer comprises at most 2 identical blocks.
De manière avantageuse le polyméthacrylate d'alkyle est le polyméthacrylate de méthyle (PMMA). Advantageously, the polyalkyl methacrylate is polymethyl methacrylate (PMMA).
Avantageusement encore, le polyacrylate d'alkyle est choisi dans le groupe constitué par le polyacrylate de butyle (PABu) et un copolymère d'acrylate de butyle et d'acrylate de 2-éthyl- héxyl. Advantageously again, the polyalkyl acrylate is chosen from the group consisting of polybutyl acrylate (PABu) and a copolymer of butyl acrylate and 2-ethylhexyl acrylate.
Plus particulièrement, le copolymère à blocs acryliques est un copolymère tri-blocs du type PMMA-PABu-PMMA. More particularly, the copolymer with acrylic blocks is a tri-block copolymer of the PMMA-PABu-PMMA type.
Dans le cadre de la présente invention, l'expression « polymère à blocs » représente un polymère dont les macromolécules sont constituées de blocs enchaînés linéairement. Les blocs peuvent être assemblés directement ou par l'intermédiaire d'une unité constitutive qui ne fait pas partie intégrante des blocs. In the context of the present invention, the expression “block polymer” represents a polymer whose macromolecules consist of linearly linked blocks. The blocks can be assembled directly or through a constituent unit which is not an integral part of the blocks.
Dans le cadre de la présente invention, l'expression « copolymère à blocs » représente un copolymère à blocs issu de plusieurs espèces de polymères. In the context of the present invention, the expression “block copolymer” represents a block copolymer resulting from several species of polymers.
Dans le cadre de la présente invention, l'expression « bloc » représente la partie d'une macromolécule comprenant une pluralité d'unités constitutives et qui possède au moins une particularité de constitution ou de configuration qui n'apparaît pas dans les parties adjacentes. In the context of the present invention, the expression “block” represents the part of a macromolecule comprising a plurality of constituent units and which has at least one peculiarity of constitution or configuration which does not appear in the adjacent parts.
L'expression « substance sémiochimique » qualifie une substance chimique émise par une plante ou un animal dans l'environnement et qui a valeur de signal entre les êtres vivants. L'expression « composition comprenant une substance sémiochimique » fait référence à une composition, typiquement une composition liquide qui comprend, ou consiste en, une ou plusieurs substances sémiochimiques, éventuellement solubilisée(s) dans un solvant.The expression “semiochemical substance” qualifies a chemical substance emitted by a plant or an animal in the environment and which has signal value between living beings. The expression “composition comprising a semiochemical substance” refers to a composition, typically a liquid composition which comprises, or consists of, one or more semiochemical substances, optionally dissolved in a solvent.
Les substances sémiochimiques sont classées en phéromones - qui permettent la communication entre des individus de la même espèce - et allomones, kairomones et synomones qui sont échangées entre des animaux ou des plantes appartenant à des espèces différentes. Les substances sémiochimiques peuvent être perçues par différents organes pour les composés volatils, ou pour les composés non volatils. Les informations portées par les sémiochimiques peuvent permettre la localisation et la reconnaissance d'un partenaire sexuel, par exemple. Semiochemicals are categorized into pheromones - which enable communication between individuals of the same species - and allomones, kairomones and synomones which are exchanged between animals or plants belonging to different species. Semiochemicals can be perceived by different organs for volatile compounds, or for non-volatile compounds. The information carried by the semiochemicals can allow the location and recognition of a sexual partner, for example.
Les substances sémiochimiques et plus particulièrement les phéromones sont des composés chimiques dont un grand nombre d'exemples (8000) est donné dans la base de données accessible en ligne Pherobase (www.pherobase.com). Semiochemicals and more particularly pheromones are chemical compounds of which a large number of examples (8000) are given in the database accessible online Pherobase (www.pherobase.com).
Selon un mode de réalisation de l'invention la substance sémiochimique est une substance sémiochimique volatile, en particulier une substance sémiochimique volatile à chaîne grasse, et est avantageusement choisie dans le groupe des phéromones, en particulier les phéromones d'insectes. According to one embodiment of the invention, the semiochemical substance is a volatile semiochemical substance, in particular a volatile semiochemical substance with a fatty chain, and is advantageously chosen from the group of pheromones, in particular insect pheromones.
De manière particulièrement préférée, la substance sémiochimique volatile est lipophile et est une phéromone à chaîne grasse. Particularly preferably, the volatile semiochemical substance is lipophilic and is a fatty chain pheromone.
Par l'expression « chaîne grasse », il est entendu au sens de la présente invention, une chaîne aliphatique hydrocarbonnée linéaire ou ramifiée, éventuellement insaturée, comportant 5 à 18, 6 à 16 ou 5 à 16 atomes de carbone, conférant ainsi un caractère lipophile à la substance sémiochimique. By the expression "fatty chain", it is understood within the meaning of the present invention, a linear or branched hydrocarbon aliphatic chain, optionally unsaturated, comprising 5 to 18, 6 to 16 or 5 to 16 carbon atoms, thus conferring a character lipophilic to the semiochemical substance.
L'expression « volatile » fait référence à l'aptitude de la substance sémiochimique à passer de l'état liquide à l'état gazeux, dans certaines conditions, c'est-à-dire aux environ 20°C et 760 mm de Hg. Un liquide « volatil » étant un liquide dont la pression de vapeur saturante à 20°C est supérieure à 0,01 mm de Hg, préférentiellement elle est comprise entre 0,01 et 20, de manière plus préférentielle entre 0,01 et 10, plus préférentiellement entre 0,01 et 5. Parmi les exemples de pheromones à chaîne grasse, des pheromones connues et utilisables selon la présente invention sont : les alkanols et alkénols volatiles ayant de 5 à 18 carbones, les alkanals et alkénals volatiles ayant de 5 à 18 carbones, les alkanones ayant de 6 à 18 carbones, le l,7-dioxaspirononane,le 3-ou 4-hydroxy-l,7-dioxaspiro-undecane, l'alcool benzytique, le Z-(9)-tricosène (muscature), héneicosène, les acides diacetyl ou alcanoïques ayant de 5 to 16 carbones tels que l'acide caprylique, l'acide laurylique, le pinène, le méthyleugenol, l'éthyldodécanoate, le tert-butyl 4-(or 5-)chloro-2-éthylcyclohexane- carboxylate, la mycrénone, la cucurbitacine, le trimédlure et le (E,E)-8,10-dodécadien-l-ol (codlémone). The expression "volatile" refers to the ability of the semiochemical substance to change from the liquid state to the gaseous state, under certain conditions, that is to say at approximately 20°C and 760 mm Hg A “volatile” liquid being a liquid whose saturation vapor pressure at 20° C. is greater than 0.01 mm Hg, preferably it is between 0.01 and 20, more preferably between 0.01 and 10 , more preferably between 0.01 and 5. Among the examples of fatty chain pheromones, known pheromones that can be used according to the present invention are: volatile alkanols and alkenols having from 5 to 18 carbons, volatile alkanals and alkenals having from 5 to 18 carbons, alkanones having from 6 to 18 carbons, l,7-dioxaspirononane, 3-or 4-hydroxy-l,7-dioxaspiro-undecane, benzyl alcohol, Z-(9)-tricosene (muscature), heneicosene, diacetyl or alkanoic acids having 5 to 16 carbons such as caprylic acid, laurylic acid, pinene, methyl eugenol, ethyldodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane- carboxylate, mycrenone, cucurbitacin, trimedlure and (E,E)-8,10-dodecadian-l-ol (codlemone).
De manière avantageuse la substance semiochimique volatile peut être choisie parmi le ferruginéol, la ferruginéone ou un mélange ferruginéol-ferruginéone. Advantageously, the volatile semiochemical substance can be chosen from ferruginol, ferruginone or a ferruginol-ferruginone mixture.
D'autres exemples de phéromones à chaîne grasse connues sont : le Z-5-Décényl acétate, le dodécanyl acétate, le Z-7- dodécényl acétate, le E-7-dodécényl acétate, le Z-8-dodécényl acétate, le E-8-dodécényl acétate, le Z-9- dodécényl acétate, le E-9-dodécényl acétate, le E- 10-dodécényl acétate, le 11-dodécényl acétate, le Z- 9,11-dodécadiényl acétate, le E-9,11- dodécadiényl acétate, le Z-11-tridécényl acétate, le E-l 1-tridécény I acétate, le tétradécényl acétate, le E-7-tétradécényl acétate, le Z-8-tétradécényl acétate, le E-8-tetradacényl acétate, le Z-9-tétradécényl acétate, le E-9-tétradécényl acétate, le Z-10-tétradécényl acétate, le E- 10-tétradécényl acétate, le Z-11-tétradécényl acétate, le E-11-tétradécényl acétate, le Z-12- pentadécényl acétate, le E-12-pentadécényl acétate, l'hexadécanyl acétate, le Z-7- hexadécényl acétate, le Z-11-hexadécényl acétate, le E-11-hexadécényl acétate, l'octadécanyl acétate, le E,Z-7,9- dodécadiényl acétate, le Z,E-7,9-dodécadiényl acetate, le E,E-7,9-dodécadiényl acétate, le Z,Z-7,9-dodécadiényl acétate, le E,E-8,10-dodécadienyl acetate, le E,Z-9,12-dodécadiényl acétate, le E,Z-4,7- tri-décadiényl acétate, le 4-méthoxy- cinnamaldéhyde, la [béta]-ionone, l'estragol, l'eugenol, I' indole, le 8-méthyl-2-décyl propanoate, le E,E-9,ll-tétradécadiényl acétate, le Z,Z-9,12-tétradécadiényl acétate, le Z,Z- 7,11-héxadécadiényl acétate, le E,Z-7,ll-héxadécadiényl acetate, le Z,E-7,ll-hexadécadiényl acétate, le E,E-7,ll-hexadécadiényl acétate, le Z,Z-ll,13-hexadécadiényl acétate le Y,Z- 11,13-hexadécadiényl acetate, le Z,E-3,13-octadécadiényl acétate, le E,Z-3,13- octadécadiényl acétate, le E,E-3,13-octadécadiényl acétate, l'hexanol, l'heptanol, l'octanol, le décanol, le Z-6-nonénol, le E-6-nonénol, le 4méthyl 5nonanol, la 4 méthyl 5 nonanone, le dodécanol, le 11-dodécénol, le Z-7-dodécénol, le E-7-dodécénol, le Z-8-dodécénol, le E-8- dodécénol, le E-9-dodécénol, le Z-9-dodécénol, le E-9,ll-dodécadiénol, le Z-9,11- dodécadiénol, le Z,E-5,7-dodécadiénol, le E,E-5,7-dodécadiénol, le E,E-8,10-dodécadiénol, le E,Z-8,10-dodécadiénol, le Z,Z-8,10-dodécadiénol, le Z,E-8,10-dodécadiénol, le E,Z-7,9- dodécadiénol, le Z,Z-7,9-dodécadiénol, le E-5-tétradécénol, le Z-8-tétradécénol, le Z-9- tétradécénol, le E-9-tetradécénol, le Z-10- tétradécénol, le Z-ll-tétradécénol, le E-ll- tétradécénol, le Z-ll-hexadécénol, le Z,E-9, 11-tétradécadiénol, le Z,E-9,12-tétradécadiénol, le Z,Z-9,12-tétradécadiénol, le Z,Z-10,12-tetradécadiénol, le Z,Z-7,ll-hexadécadiénol, Z,E- 7,11-hexadecadiénol, (E)-14-méthyl-8-hexadécén-l-ol, le (Z)-14-méthyl-8-hexadécén-l-ol, le E,E-10,12-hexadécadiénol, le E,Z-10,12-hexadécadiénol, le dodécanal, le Z- 9-dodécénal, le tétradécanal, le Z-7-tétradécénal, le Z-9-tétradécénal, le Z-ll-tétradécénal, le E-ll- tétradécénal, le E-ll,13-tétradécadiénal, le E,E-8,10-tétradécadiénal, le Z, E-9,11- tétradécadiénal, le Z, E-9,12-tétradécadiénal, l'hexadécanal, le Z-8-hexadécénal, le Z-9- hexadécénal, le Z-10-hexadécénal, le E-10-hexadécénal, le Z-ll-hexadécénal, le E-ll- hexadécénal, le Z-12-hexadécénal, le Z-13-hexadécénal, le (Z)-14-méthyl-8-hexadécénal, le (E)-14-méthyl-8-hexadécénal, le Z,Z-7, 11-hexadécadiénal, le Z, E-7, 11-hexadécadiénal, le Z,E-9, 11-hexadécadiénal, le E,E-10, 12-hexadécadiénal, le E,Z-10, 12-hexadécadiénal, le Z, E- 10,12-hexadécadiénal, le Z,Z-10,12-hexadécadiénal, le Z,Z-11, 13-hexadécadiénal, l'octadécanal, le Z-ll-octadécénal, le E-13-octadécénal, le Z-13-octadécénal, le Z-5-décényl- 3-méthyl butanoate, la disparlure: (+) cis-7,8-epoxy-2-methyloctadecane, le seudénol: 3- methyl-2-cyclohexen-l-ol, le sulcatol : 6-methyl-5-hepten-2-ol, l'ipsénol: 2-methyl-6- methylene-7- octen-4-ol, l'ipsdiénol: 2-methyl-6-methylene-2, 7-octadien-4-ol, la grandiure I : cis-2-isopropenyl-l-methylcyclobutane-ethanol, la grandiure II : Z-3,3-dimethyl-l- cyclohexane-ethanol, la grandiure III : Z-3,3-dimethyl-l-cyclohexane-acataldéhyde, la grandiure IV: E-3,3-diméthyl-l-cyclohexane- acétaldéhyde, cis-2-ver-benol: cis-4,6,6- triméthylbicyclo[3, l,l]hept-3-en-2-ol, la cucurbitacine, 2- méthyl-3-buten-2-ol, 4-méthyl-3- heptanol, la cucurbitacine, 2-méthyl-3-buten-2-ol, 4-méthyl-3- heptanol, l'[alpha]-pinène: 2,6,6-triméthylbicyclo[3, l,l]hepten-2-ène, l'[alpha]-caryophyllène: 4, ll,ll-triméthyl-8- méthylène-bicyclo[7,2,0]undécane, le Z-9-tricosène, l'[al pha]-multistriatine, le 2-(2-endo,4- endo)-5-éthyl-2,4-diméthyl-6,8-dioxabicyclo [3,2,1] octane, le méthyleugénol: 1,2- dimethoxy-4-(2-propenyl)phenol, la linéatine: 3,3,7-triméthyl-2,9-dioxatricyclo [3,3, 1,0] nonane, le chalcogran : 2-éthyl-l,6-dioxaspiro[4,4]nonane, la frontaline : l,5-diméthyl-6,8- dioxabicyclo[3,2, l]octane, l'endo-brevicomine : endo-7-éthyl-5-méthyl-6,8- dioxabicyclo[3,2,l]octane, l'exo-brévicomine : exo-7-éthyl-5-méthyl-6,8- dioxabicyclo[3,2,l]octane, la (Z)-5-(l-décényl)dihydro-2-(3H)-furanone, le farnésol : 3,7,11- triméthyl-2,6, le 10-dodécatrien-l-ol, le nérolidol 3,7-ll-triméthyl-l,6,10-dodécatrién-3-ol, le 3-méthyl,6-(l-méthyléthényl)-9-décen-l-ol acétate, le (Z)-3-méthyl-6-(l-méthyléthényl)- 3, le 9-décadién-l-ol acétate, le (E)-3,9-méthyl-6-(l-méthyl-éthényl)-5,8-décadién-l-ol acétate, le 3- méthylène-7-méthyl-octen-l-ol propionate, le (Z)-3,7-diméthyl-2,7-octadién-l- ol propionate, (Z)-3,9-diméthyl-6-(l-méthyl-éthényl)-3, 9-décadién-l-ol. Other examples of known fatty chain pheromones are: Z-5-Decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E -8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9 ,11-dodecadienyl acetate, Z-11-tridecenyl acetate, El 1-tridecenyl I acetate, tetradecenyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetradacenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate, Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z -12- pentadecenyl acetate, E-12-pentadecenyl acetate, hexadecanyl acetate, Z-7-hexadecenyl acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanyl acetate, E ,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E, E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate, E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate, E,Z- 4,7-tri-decadienyl acetate, 4-methoxy-cinnamaldehyde, [beta]-ionone, estragole, eugenol, indole, 8-methyl-2-decyl propanoate, E,E- 9,ll-tetradecadienyl acetate, Z,Z-9,12-tetradecadienyl acetate, Z,Z-7,11-hexadecadienyl acetate, E,Z-7,ll-hexadecadienyl acetate, Z,E-7, ll-hexadecadienyl acetate, E,E-7,ll-hexadecadienyl acetate, Z,Z-ll,13-hexadecadienyl acetate, Y,Z-11,13-hexadecadienyl acetate, Z,E-3,13-octadecadienyl acetate, E,Z-3,13- octadecadienyl acetate, E,E-3,13-octadecadienyl acetate, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E -6-nonenol, 4methyl 5nonanol, 4 methyl 5 nonanone, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol, E,Z-8,10-dodecadienol, Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7 ,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E- ll- tetradecenol, Z-ll-hexadecenol, Z,E-9, 11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10 ,12-tetradecadienol, Z,Z-7,ll-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-l-ol, (Z)-14-methyl -8-Hexadecen-l-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecanal, Z-7-tetradecenal , Z-9-tetradecenal, Z-ll-tetradecenal, E-ll-tetradecenal, l e E-11,13-tetradecadienal, E,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal, Z,E-9,12-tetradecadienal, hexadecanal, Z-8 -hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-ll-hexadecenal, E-ll-hexadecenal, Z-12-hexadecenal, Z-13- hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, Z,Z-7, 11-hexadecadienal, Z,E-7, 11-hexadecadienal, Z,E-9, 11-hexadecadienal, E,E-10, 12-hexadecadienal, E,Z-10, 12-hexadecadienal, Z,E- 10,12-hexadecadienal, Z,Z-10 ,12-hexadecadienal, Z,Z-11,13-hexadecadienal, octadecanal, Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3- methyl butanoate, disparlure: (+) cis-7,8-epoxy-2-methyloctadecane, seudenol: 3-methyl-2-cyclohexen-l-ol, sulcatol: 6-methyl-5-hepten-2-ol , ipsenol: 2-methyl-6-methylene-7- octen-4-ol, ipsdienol: 2-methyl-6-methylene-2, 7-octadien-4-ol, grandure I: cis-2 -isopropenyl-l-methylcyclob utane-ethanol, size II: Z-3,3-dimethyl-l-cyclohexane-ethanol, size III: Z-3,3-dimethyl-l-cyclohexane-acataldehyde, size IV: E-3,3- dimethyl-l-cyclohexane-acetaldehyde, cis-2-ver-benol: cis-4,6,6-trimethylbicyclo[3,l,l]hept-3-en-2-ol, cucurbitacin, 2-methyl-3 -buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [alpha]-pinene: 2.6, 6-trimethylbicyclo[3,1,1]hepten-2-ene, [alpha]-caryophyllene: 4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane, Z-9 -tricosene, [alpha]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo [3,2,1] octane, methyl eugenol: 1,2- dimethoxy-4-(2-propenyl)phenol, lineatin: 3,3,7-trimethyl-2,9-dioxatricyclo [3,3, 1,0] nonane, chalcogran: 2-ethyl -l,6-dioxaspiro[4,4]nonane, frontalin: l,5-dimethyl-6,8- dioxabicyclo[3,2,l]octane, endo-brevicomin: endo-7-ethyl-5-methyl-6,8- dioxabicyclo[3,2,l]octane, exo-brevicomin: exo-7- ethyl-5-methyl-6,8-dioxabicyclo[3,2,l]octane, (Z)-5-(l-decenyl)dihydro-2-(3H)-furanone, farnesol: 3,7,11 - 2,6-trimethyl, 10-dodecatrien-l-ol, nerolidol 3,7-ll-trimethyl-l,6,10-dodecatrien-3-ol, 3-methyl,6-(l-methylethenyl) -9-decen-l-ol acetate, (Z)-3-methyl-6-(l-methylethenyl)-3, 9-decadien-l-ol acetate, (E)-3,9-methyl- 6-(l-methyl-ethenyl)-5,8-decadien-l-ol acetate, 3-methylene-7-methyl-octen-l-ol propionate, (Z)-3,7-dimethyl-2, 7-octadien-1-ol propionate, (Z)-3,9-dimethyl-6-(1-methyl-ethenyl)-3,9-decadien-1-ol.
Comme indiqué, selon un mode de réalisation, la substance sémiochimique est choisie dans le groupe des phéromones, en particulier parmi les phéromones sexuelles d'insectes, en particulier les phéromones sexuelles d'insectes à chaîne grasse, et plus particulièrement encore dans le groupe constitué par les phéromones des papillons des processionnaires du pin, les phéromones des papillons des processionnaires du chêne, les phéromones de la pyrale du buis, les phéromones des bombyx, les phéromones des carpocapses, les phéromones de la mouche du pêcher, les phéromones de la sésamie du maïs, les phéromones de l'eudémis, les phéromones de la batrachédra, les phéromones de la miride du cacaoyer, les phéromones des charançons des palmiers ou du bananier, les phéromones de l'eudémis et les phéromones de la cochylis de la vigne ainsi que leurs mélanges. As indicated, according to one embodiment, the semiochemical substance is chosen from the group of pheromones, in particular from insect sex pheromones, in particular fatty chain insect sex pheromones, and more particularly still from the group consisting by pine processionary moth pheromones, oak processionary moth pheromones, boxwood moth pheromones, moth pheromones, codling moth pheromones, peach fly pheromones, sesame pheromones maize, eudemis pheromones, batrachedra pheromones, cocoa mirid pheromones, palm or banana weevil pheromones, eudemis pheromones and vine cochylis pheromones as well as than their mixtures.
Comme évoqué plus avant et selon un mode de réalisation préféré, la substance sémiochimique, en particulier volatile, en particulier encore à chaîne grasse, peut-être une phéromone sexuelle d'insectes. As mentioned above and according to a preferred embodiment, the semiochemical substance, in particular volatile, in particular still with a fatty chain, may be an insect sex pheromone.
Ainsi, selon un mode de réalisation de l'invention, la méthode selon l'invention est caractérisée en ce que l'étape d.) de diffusion de ladite substance sémiochimique depuis la composition solide imprégnée est réalisée dans le lieu de mise à disposition, en particulier une parcelle agricole, et que la méthode permet de protéger ladite parcelle contre les insectes ravageurs. Thus, according to one embodiment of the invention, the method according to the invention is characterized in that step d.) of diffusion of said semiochemical substance from the impregnated solid composition is carried out in the place of provision, in particular an agricultural plot, and that the method makes it possible to protect said plot against insect pests.
Avantageusement la composition solide est solidaire d'un support pour faciliter la mise à disposition dans une parcelle. Cette mise à disposition peut être temporaire ou pour une plus longue durée. Ainsi, avantageusement, pour la protection des parcelles, un support comprend un article qui peut être choisi dans le groupe comprenant un piquet, un tuteur, une clôture, une palissade, agrafe, crochet, une plaque, par exemple, qui pourra être fixé en un ou plusieurs points de la parcelle, et y demeurant pour la saison voire plus. De tels articles et supports peuvent être revêtus de la composition solide selon l'invention et servir de diffuseur du composé sémiochimique au sein de la parcelle. Ces articles pourront être récupérés pour rechargement ou recyclage ou entreposage en fin de saison. Advantageously, the solid composition is integral with a support to facilitate the provision in a parcel. This provision may be temporary or for a longer period. Thus, advantageously, for the protection of the plots, a support comprises an article which can be chosen from the group comprising a stake, a stake, a fence, a palisade, staple, hook, a plate, for example, which can be fixed in one or more points of the parcel, and remaining there for the season or even longer. Such articles and supports can be coated with the solid composition according to the invention and serve as a diffuser for the semiochemical compound within the plot. These items may be recovered for reloading or recycling or storage at the end of the season.
Aussi, un support comprend un article qui peut être choisi dans le groupe comprenant plaque en carton, plaque en verre, plaque en plastique, plaque métallique, chiffon, bâche, t- shirt ou tissu, par exemple. Ainsi, un tel support, par exemple un article sous forme de cartonnette ou plaque, revêtu de la composition solide selon l'invention peut être disposé à intervalle régulier au sein de la parcelle et réaliser la diffusion ; et pourra être récupéré pour rechargement ou recyclage ou entreposage en fin de saison. Also, a support comprises an article which can be chosen from the group comprising cardboard plate, glass plate, plastic plate, metal plate, cloth, tarpaulin, t-shirt or fabric, for example. Thus, such a support, for example an article in the form of cardboard or plate, coated with the solid composition according to the invention can be placed at regular intervals within the parcel and carry out the diffusion; and can be recovered for reloading or recycling or storage at the end of the season.
Les phéromones selon l'invention sont des phéromones naturelles ou de synthèse. The pheromones according to the invention are natural or synthetic pheromones.
Dans un mode de réalisation particulier de l'invention, la substance sémiochimique pourra être protégée contre l'action de la lumière et/ou celle de l'oxygène. En effet, lorsque les articles diffuseurs selon l'invention sont utilisés dans des cultures pendant plusieurs mois, il pourra être préférable de protéger la substance sémiochimique d'une altération dans le temps. L'homme du métier a l'habitude d'additionner des antioxydants et des anti-UV aux substances sémiochimiques pour remplir cette fonction. Un avantage du procédé selon l'invention est que les stabilisants UV ou les antioxydants peuvent être déjà contenus dans la composition liquide avant son application sur un support ou son imprégnation par le compose sémiochimique ou bien ajoutés à la composition comprenant la substance sémiochimique avant que celle-ci ne soit incorporée/adsorbée dans/par la composition polymérique. Ces deux méthodes assurent une protection intime de la substance sémiochimique jusqu'à sa diffusion dans le milieu extérieur. In a particular embodiment of the invention, the semiochemical substance may be protected against the action of light and/or that of oxygen. Indeed, when the diffuser articles according to the invention are used in cultures for several months, it may be preferable to protect the semiochemical substance from an alteration over time. Those skilled in the art are accustomed to adding antioxidants and anti-UV to semiochemical substances to fulfill this function. An advantage of the process according to the invention is that the UV stabilizers or the antioxidants can already be contained in the liquid composition before its application to a support or its impregnation with the semiochemical compound or else added to the composition comprising the semiochemical substance before that -it is incorporated / adsorbed in / by the polymeric composition. These two methods ensure intimate protection of the semiochemical until it is released into the external environment.
Les antioxydants peuvent être choisis dans le groupe constitué par la vitamine E, l'hydroxyanisole buty lé(BHA), l'hydroxytoluène butylé (BHT) utilisés seuls ou en mélange. Ces antioxydants protègent la substance sémiochimique de la dégradation et peuvent être ajoutés dans des quantités, en pourcentage en poids de la composition liquide ou solide, allant de 0,1% environ à 3% environ, particulièrement entre 0.5 et 2%. The antioxidants can be chosen from the group consisting of vitamin E, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) used alone or as a mixture. These antioxidants protect the semiochemical from degradation and can be added in amounts, in percentage by weight of the liquid or solid composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5 and 2%.
Les additifs anti-UV peuvent être choisis dans le groupe constitué par le béta-carotène, l'acide p-aminobenzoïque, les amines encombrées et les alkoxyamines encombrées utilisés seuls ou en mélange. Ces anti-UV protègent les sémiochimques de la dégradation par la lumière et peuvent être ajoutés dans des quantités, en pourcentage en poids de la composition, allant de 0,1% environ à 3% environ, particulièrement entre 0.5 et 2%. The anti-UV additives can be chosen from the group consisting of beta-carotene, p-aminobenzoic acid, hindered amines and hindered alkoxyamines used alone or as a mixture. These UV stabilizers protect the semiochemicals from degradation by light and can be added in quantities, as a percentage by weight of the composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5 and 2%.
La présente invention vise aussi une composition liquide comprenant au moins une résine polymérique, au moins un solvant, optionnellement au moins un pigment, optionnellement au moins une charge, optionnellement au moins une substance sémiochimique et au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle. The present invention also relates to a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, optionally at least one semiochemical substance and at least one copolymer with acrylic blocks, said copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block.
Une telle composition liquide se présente ainsi sous la forme d'une composition de type peinture ou encre pour revêtement de surface qui permet l'enduction d'un support. Such a liquid composition is thus in the form of a composition of the paint or ink type for surface coating which allows the coating of a support.
Par enduction on entend ici, que la composition liquide est appliquée sur un support solide qui va être revêtu en partie ou totalement par la composition liquide qui sera solidifiée suite à l'évaporation du solvant et formera la composition solide. By coating is meant here that the liquid composition is applied to a solid support which will be partially or totally coated with the liquid composition which will be solidified following the evaporation of the solvent and will form the solid composition.
Un autre avantage de la composition selon l'invention est en effet qu'elle peut être appliquée sur toute forme d'objet. Another advantage of the composition according to the invention is in fact that it can be applied to any form of object.
En effet son caractère liquide (ou fluide) permet de l'appliquer sur toute surface et de recouvrir tout ou partie d'un support, donné. Ainsi il est possible de l'appliquer sur un support solide ou souple tel qu'un collier, un tissu, un piquet, une barre, une plaque ou une plaquette en tout matériau par exemple, et ce en rapport avec le mode d'utilisation et le lieu de diffusion envisagé. In fact, its liquid (or fluid) nature makes it possible to apply it to any surface and to cover all or part of a given support. Thus it is possible to apply it on a solid or flexible support such as a collar, a fabric, a stake, a bar, a plate or a plate in any material for example, and this in relation to the mode of use. and the intended venue.
L'application peut être réalisée au rouleau, au pinceau, par pulvérisation, par trempage ou par tout autre moyen adapté permettant de revêtir le support en toute ou partie par la composition fluide. La facilité d'application de la composition liquide selon l'invention permet aussi de l'utiliser comme une peinture ou une encre et réaliser toute application sur tout support, en particulier textile, pour le recouvrir en totalité ou en partie en définissant des logos ou des inscriptions et ce selon la volonté ou le désir de l'utilisateur. The application can be carried out with a roller, a brush, by spraying, by dipping or by any other suitable means making it possible to coat the support in whole or in part with the fluid composition. The ease of application of the liquid composition according to the invention also makes it possible to use it as a paint or an ink and to carry out any application on any support, in particular textiles, to cover it in whole or in part by defining logos or registrations and this according to the will or the desire of the user.
Ainsi la composition liquide selon l'invention peut être utilisée dans une méthode d'impression par les techniques de sérigraphie connues de l'homme du métier et ce pour sérigraphier tout support de son choix et ce quel que soit la matière, par exemple sur textile pour obtenir des articles revêtus tels que des vêtements, des jouets ou tout ustensile par exemple. Thus the liquid composition according to the invention can be used in a method of printing by screen printing techniques known to those skilled in the art and this for screen printing any support of their choice and this whatever the material, for example on textile to obtain coated articles such as clothes, toys or any utensil for example.
La composition liquide se solidifie ensuite via l'évaporation du solvant ce qui permet d'obtenir une composition solide sous la forme d'un revêtement de surface comprenant, ou constitué de, une phase continue de résine polymérique dans laquelle est dispersé le pigment optionnel , la charge optionnelle, le au moins un copolymère à blocs acryliques optionnel, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle, ainsi que la substance sémiochimique optionnelle. The liquid composition then solidifies via the evaporation of the solvent, which makes it possible to obtain a solid composition in the form of a surface coating comprising, or consisting of, a continuous phase of polymeric resin in which the optional pigment is dispersed, the optional filler, the at least one optional acrylic block copolymer, said acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, as well as the optional semiochemical substance.
La composition liquide selon l'invention est aussi caractérisée en ce que la substance sémiochimique représente entre 0 % et 80% en poids de la composition liquide, particulièrement entre 1 et 60%, plus particulièrement encore entre 5 et 50%. The liquid composition according to the invention is also characterized in that the semiochemical substance represents between 0% and 80% by weight of the liquid composition, particularly between 1 and 60%, more particularly still between 5 and 50%.
Les supports, tels que des articles comme évoqués plus avant, revêtus de la composition solide selon l'invention, si elle ne contient pas déjà le composé sémiochimique, peuvent ensuite être imprégnés et chargés par une composition comprenant une substance sémiochimique. The supports, such as articles as mentioned above, coated with the solid composition according to the invention, if it does not already contain the semiochemical compound, can then be impregnated and loaded with a composition comprising a semiochemical substance.
Cette imprégnation, ou chargement, peut être réalisée par simple mise en contact de la composition solide selon l'invention avec une composition comprenant un composé sémiochimique. En particulier la composition comprenant ledit composé sémiochimique est sous la forme d'une composition liquide comprenant ledit composé sémiochimique et qui est mise en contact avec la composition solide. Une telle mise en contact peut être réalisée par vaporisation d'une composition liquide comprenant le composé sémiochimique, mais aussi par badigeonnage au pinceau ou au rouleau ou par trempage par exemple. This impregnation, or loading, can be carried out by simply bringing the solid composition according to the invention into contact with a composition comprising a semiochemical compound. In particular, the composition comprising said semiochemical compound is in the form of a liquid composition comprising said semiochemical compound and which is brought into contact with the solid composition. Such bringing into contact can be carried out by vaporization of a liquid composition comprising the semiochemical compound, but also by painting with a brush or a roller or by dipping, for example.
Il va de soi que compte tenu des prix des substances sémiochimiques, on favorisera une application permettant de limiter les pertes et ainsi une application par aspersion, pulvérisation sera plus avantageuse. It goes without saying that, taking into account the prices of semiochemical substances, an application which makes it possible to limit losses will be favored and thus an application by sprinkling, spraying will be more advantageous.
Un autre avantage particulièrement important de la composition selon l'invention est que la composition solide peut être chargée ou rechargée par une substance sémiochimique, telle qu'une phéromone. Another particularly important advantage of the composition according to the invention is that the solid composition can be charged or re-charged with a semiochemical substance, such as a pheromone.
En effet, une fois que la quantité initiale de composé sémiochimique, absorbée par la composition solide -ou initialement présente dans la composition liquide - a été relarguée et diffusée, il est possible de récupérer la composition solide ou le support revêtu de la composition solide selon l'invention (et ce quelle que soit sa forme) et de ré-imprégner ladite composition de sémiochimique selon le procédé décrit plus avant. De même, par exemple, un mur recouvert par la composition solide selon l'invention pourra être réimprégné en une composition comprenant une substance sémiochimique par mise en contact comme expliqué plus avant, par exemple par vaporisation. Indeed, once the initial quantity of semiochemical compound, absorbed by the solid composition - or initially present in the liquid composition - has been released and diffused, it is possible to recover the solid composition or the support coated with the solid composition according to the invention (and whatever its form) and to re-impregnate said semiochemical composition according to the method described above. Likewise, for example, a wall covered with the solid composition according to the invention may be reimpregnated with a composition comprising a semiochemical substance by bringing it into contact as explained further on, for example by vaporization.
Ainsi c'est aussi un objet de l'invention que de fournir un procédé de fabrication d'une composition solide selon l'invention chargée en une substance sémiochimique, comprenant les étapes suivantes : Thus, it is also an object of the invention to provide a method for manufacturing a solid composition according to the invention loaded with a semiochemical substance, comprising the following steps:
- fournir une composition solide comprenant une résine polymérique constituant une phase continue dans laquelle est dispersé et immobilisé au moins un copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle, une charge optionnelle et un pigment optionnel ; - providing a solid composition comprising a polymeric resin constituting a continuous phase in which is dispersed and immobilized at least one acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, an optional filler and a optional pigment;
- mettre en contact ladite composition avec une composition comprenant une substance sémiochimique pendant un temps et à une température permettant l'imprégnation de ladite composition solide par ladite substance, - bringing said composition into contact with a composition comprising a semiochemical substance for a time and at a temperature allowing the impregnation of said solid composition by said substance,
- récupérer ladite composition solide imprégnée de substance sémiochimique. La composition solide selon l'invention est aussi caractérisée en ce qu'une fois imprégnée par la substance sémiochimique, celle-ci représente entre 1% et 80 % en poids de la composition solide, particulièrement entre 1 et 50%, entre5 et 50%, plus particulièrement encore entre 5 et 40%, voire encore entre 5 et 30%, ou encore entre 5 et 20%. - recovering said solid composition impregnated with semiochemical substance. The solid composition according to the invention is also characterized in that once impregnated with the semiochemical substance, the latter represents between 1% and 80% by weight of the solid composition, particularly between 1 and 50%, between 5 and 50% , more particularly between 5 and 40%, or even between 5 and 30%, or even between 5 and 20%.
Une composition solide selon l'invention peut ainsi diffuser et libérer progressivement la substance sémiochimique dans l'environnement jusqu'à épuisement de la quantité de substance sémiochimique contenue. Elle peut ensuite être réutilisée pour un rechargement comme décrit ci-avant, puis une nouvelle diffusion. Et cela peut être répété plusieurs fois.A solid composition according to the invention can thus diffuse and gradually release the semiochemical substance into the environment until the quantity of semiochemical substance contained is exhausted. It can then be reused for reloading as described above, then a new broadcast. And this can be repeated several times.
Un tel avantage est très important car il permet de recycler les supports revêtus, par exemple des articles, de la composition solide, ce qui a un sens tant économique qu'écologique. Such an advantage is very important because it makes it possible to recycle the supports coated, for example articles, with the solid composition, which makes both economic and ecological sense.
Le copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle se retrouve dispersé au sein de la phase continue de résine sous la forme d'inclusions qui vont contribuer à capter, absorber, retenir et relarguer la substance sémiochimique. The copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block is found dispersed within the continuous resin phase in the form of inclusions which will contribute to capturing, absorbing, retaining and release the semiochemical.
L'invention vise ainsi une composition solide selon l'invention, caractérisé en ce que la résine polymérique constitue une phase continue dans laquelle est dispersé et immobilisé le au moins un copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle, la charge optionnelle et le pigment optionnel. The invention thus relates to a solid composition according to the invention, characterized in that the polymeric resin constitutes a continuous phase in which is dispersed and immobilized the at least one copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least a polyalkylacrylate block, the optional filler and the optional pigment.
Enfin, l'invention concerne enfin l'utilisation d'une composition solide ou liquide selon l'invention comprenant au moins une substance sémiochimique pour la diffusion de ladite substance sémiochimique. Finally, the invention finally relates to the use of a solid or liquid composition according to the invention comprising at least one semiochemical substance for the diffusion of said semiochemical substance.
L'invention vise enfin l'utilisation d'une composition solide ou liquide selon l'invention pour l'absorption et la diffusion d'une substance sémiochimique. The invention finally relates to the use of a solid or liquid composition according to the invention for the absorption and diffusion of a semiochemical substance.
EXEMPLES EXAMPLES
Matériaux et matières premières : Les matériaux copolymères à blocs sont des matériaux de la gamme nanostrenth® vendu par Arkema comme par exemple le M53, M65 ou le M53F. Les phéromones sont synthétisées par M2i Development ou M2i Salin selon des méthodes déjà reportées dans la littérature. La phéromone de la Lobesia Botrana (Eudémis de la vigne) est le 7E,9Z- dodecadienylacetate (CAS : 54364-62-4) de masse molaire 224,34 g/mol. Le laurate de méthyle (CAS 111-82-0) de masse molaire 214,34 g/mol est un des composants de la composition phéromonale apaisante de l'ADAPTIL®. Les encres commerciales sont achetées chez TIFLEX. Materials and raw materials: Block copolymer materials are materials from the nanostrenth® range sold by Arkema, such as M53, M65 or M53F, for example. The pheromones are synthesized by M2i Development or M2i Salin according to methods already reported in the literature. The pheromone of Lobesia Botrana (Eudemis de la vigne) is 7E,9Z-dodecadienylacetate (CAS: 54364-62-4) with a molar mass of 224.34 g/mol. Methyl laurate (CAS 111-82-0) with a molar mass of 214.34 g/mol is one of the components of the soothing pheromone composition of ADAPTIL®. Commercial inks are purchased from TIFLEX.
Exemple 1 : Démonstration de l'effet de rétention sur des films de copolymères blocs : Une solution de copolymère à bloc M53 dans l'acétate d'éthyle est préparée à 20% poids. Au moyen d'une pipette en verre, lOmL de solution sont déposés dans une barquette en aluminium de 10 cm de diamètre. La barquette est placée dans une étuve ventilée pendant 24 h. Un film homogène de copolymère à bloc est obtenu. 10 barquettes sont ainsi préparées et numérotées de 1 à 20. Example 1: Demonstration of the retention effect on films of block copolymers: A solution of block copolymer M53 in ethyl acetate is prepared at 20% by weight. Using a glass pipette, lOmL of solution is placed in an aluminum tray 10 cm in diameter. The tray is placed in a ventilated oven for 24 h. A homogeneous film of block copolymer is obtained. 10 trays are thus prepared and numbered from 1 to 20.
Sur les barquettes numérotées de 1 à 5 sont déposés 100 mg de phéromone de la lobésia (7E,9Z-dodecadienylacetate). Sur celles numérotées de 6 à 10, sont déposés 100 mg de laurate de méthyle. Les deux actifs sont appliqués sur le film au moyen d'un spray de solution de phéromones diluées à 20% dans le pentane. Les barquettes sont laissées à l'air libre jusqu'à la disparition visuelle de l'actif. Les barquettes sont déposées dans une étuve ventilée maintenue à 40°C (lobesia) ou 30°C (méthyl laurate). Deux barquettes vierges sont chargées avec la même quantité de chaque actif. On trays numbered from 1 to 5 are placed 100 mg of lobesia pheromone (7E,9Z-dodecadienylacetate). On those numbered from 6 to 10, are deposited 100 mg of methyl laurate. The two active ingredients are applied to the film using a spray of pheromone solution diluted to 20% in pentane. The trays are left in the open air until the visual disappearance of the active ingredient. The trays are placed in a ventilated oven maintained at 40°C (lobesia) or 30°C (methyl laurate). Two blank trays are loaded with the same amount of each active.
Les barquettes sont régulièrement analysées pour déterminer le taux de phéromone résiduel (par simple pesée ou préférentiellement par chromatographie gazeuse). The trays are regularly analyzed to determine the level of residual pheromone (by simple weighing or preferably by gas chromatography).
Dans le tableau 1 suivant est reporté le temps de diffusion en étuve nécessaire pour arriver en dessous de 10% d'actif résiduel par rapport à la quantité introduite. Table 1 below shows the diffusion time in the oven necessary to reach below 10% of residual active ingredient with respect to the quantity introduced.
[Table 1]
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0003
[Table 1]
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000020_0003
Cet exemple montre l'effet de rétention d'une surface traitée par un dépôt de fi m de copolymères à bloc par rapport à une surface non traitée. This example shows the retention effect of a surface treated with a deposition of fi m of block copolymers compared with an untreated surface.
Exemple 2 : Démonstration de l'effet du copobloc par comparaison d'une encre non- additivée de copolymères blocs avec une encre additivée. Example 2: Demonstration of the effect of the copobloc by comparison of an ink not containing additives of block copolymers with an ink containing additives.
Des plaques de verre carrées de 10 cm de côté sont imprimées par sérigraphie traditionnelle avec deux encres commerciales de type polyworks (TIFLEX) et vinylique (TIFLEX) de couleur bleue. Une série de plaques est utilisée sans traitement tandis que l'autre série est traitée en sprayant une solution de copolymères blocs M53 à 10%. Une fois séchées, ces plaques ne présentent pas de différence visuelle avec les plaques non traitées. Square glass plates with a side of 10 cm are printed by traditional screen printing with two commercial inks of the polyworks (TIFLEX) and vinyl (TIFLEX) type, blue in color. A series of plates is used without treatment while the other series is treated by spraying a 10% solution of M53 block copolymers. Once dried, these plates show no visual difference with the untreated plates.
Sur les quatre séries de plaques, sont sprayés de la phéromone de lobésia et du laurate de méthyle en solution à 20% dans du pentane. Les plaques sont laissées à l'air puis mises à diffuser en étuve ventilée respectivement à 30 °C et 40°C pour les plaques imprégnées de phéromone de lobésia et les plaques imprégnées de laurate de méthyle. Les barquettes sont régulièrement analysées pour déterminer le taux de phéromone résiduel (par simple pesée ou préférentiellement par chromatographie gazeuse). The four series of plates are sprayed with lobesia pheromone and methyl laurate in a 20% solution in pentane. The plates are left in the air and then placed in a ventilated oven at 30° C. and 40° C. respectively for the plates impregnated with lobesia pheromone and the plates impregnated with methyl laurate. The trays are regularly analyzed to determine the level of residual pheromone (by simple weighing or preferably by gas chromatography).
Dans le tableau 2 suivant est reporté le temps de diffusion en étuve nécessaire pour arriver en dessous de 10% d'actif résiduel par rapport à la quantité introduite. Table 2 below shows the diffusion time in the oven necessary to reach below 10% of residual active ingredient with respect to the quantity introduced.
[Table 2]
Figure imgf000020_0002
Figure imgf000021_0001
copolymères à blocs par rapport à une surface non traitée et une surface enduite d'encre. [Table 2]
Figure imgf000020_0002
Figure imgf000021_0001
block copolymers versus an untreated surface and an ink-coated surface.

Claims

REVENDICATIONS
1. Méthode de diffusion d'une substance sémiochimique comprenant les étapes suivantes : a. fourniture d'une composition solide comprenant une résine polymérique, une charge optionnelle et un pigment optionnel, b. Mise en contact d'une composition comprenant une substance sémiochimique avec la composition solide, c. Imprégnation de la composition solide par la composition comprenant la susbtance sémiochimique, d. Diffusion de ladite substance sémiochimique depuis la composition solide, e. optionnellement répétition des étapes b à d, caractérisé en ce que la composition solide comprenant une résine polymérique comprend en outre au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle ; ledit copolymère étant dispersé et immobilisé dans la résine polymérique, et caractérisée en outre en ce que l'étape a) est précédée des étapes al) à a3) ; l'étape al) comprenant la fourniture d'une composition liquide comprenant au moins une résine polymérique, au moins un solvant, optionnellement au moins un pigment, optionnellement au moins une charge et au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle ; l'étape a2) comprenant l'application de la composition liquide sur un support et l'étape a3) comprenant l'évaporation du solvant. 1. Method of diffusion of a semiochemical substance comprising the following steps: a. providing a solid composition comprising a polymeric resin, an optional filler and an optional pigment, b. contacting a composition comprising a semiochemical substance with the solid composition, c. Impregnation of the solid composition with the composition comprising the semiochemical substance, d. Diffusion of said semiochemical substance from the solid composition, e. optionally repeating steps b to d, characterized in that the solid composition comprising a polymeric resin further comprises at least one copolymer with acrylic blocks, the said copolymer with acrylic blocks comprising at least one polyalkyl methacrylate block and at least one polyacrylate block alkyl; said copolymer being dispersed and immobilized in the polymeric resin, and further characterized in that step a) is preceded by steps a1) to a3); step a1) comprising providing a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block; step a2) comprising the application of the liquid composition to a support and step a3) comprising the evaporation of the solvent.
2. Méthode selon la revendication 1, caractérisée en ce que la composition solide est solidaire d'un support, en particulier sous la forme d'une couche mince. 2. Method according to claim 1, characterized in that the solid composition is integral with a support, in particular in the form of a thin layer.
3. Méthode selon la revendication 2, caractérisée en ce que le support est en une matière choisie dans le groupe comprenant verre, textile, papier, carton, plastique, brique, cuir, bois, fibres végétales, métal et céramique. 3. Method according to claim 2, characterized in that the support is made of a material chosen from the group comprising glass, textile, paper, cardboard, plastic, brick, leather, wood, plant fibers, metal and ceramic.
4. Méthode selon l'une des revendications 1 à 3, caractérisée en ce que le copolymère à blocs acryliques est un copolymère bi-blocs ou un copolymère tri-blocs. 4. Method according to one of claims 1 to 3, characterized in that the acrylic block copolymer is a bi-block copolymer or a tri-block copolymer.
5. Méthode selon l'une des revendications 1 à 4, caractérisée en ce que le copolymère tri- blocs comprend au plus 2 blocs identiques. 5. Method according to one of claims 1 to 4, characterized in that the triblock copolymer comprises at most 2 identical blocks.
6. Méthode selon l'une des revendications 1 à 5, caractérisée en ce que le polyméthacrylate d’alkyle est le polyméthacrylate de méthyle (PMMA). 6. Method according to one of claims 1 to 5, characterized in that the polyalkyl methacrylate is polymethyl methacrylate (PMMA).
7. Méthode selon l'une des revendications 1 à 6, caractérisée en ce que le polyacrylate d'alkyle est choisi dans le groupe constitué par le polyacrylate de butyle (PABu) et un copolymère d'acrylate de butyle et d'acrylate de 2-éthyl-héxyl. 7. Method according to one of claims 1 to 6, characterized in that the polyalkyl acrylate is chosen from the group consisting of polybutyl acrylate (PABu) and a copolymer of butyl acrylate and acrylate of 2 -ethyl-hexyl.
8. Méthode selon l'une des revendications 1 à 7, caractérisée en ce que le copolymère à blocs acryliques est un copolymère tri-blocs du type PMMA-PABu-PMMA. 8. Method according to one of claims 1 to 7, characterized in that the copolymer with acrylic blocks is a tri-block copolymer of the PMMA-PABu-PMMA type.
9. Méthode selon l'une des revendications 1 à 8, caractérisée en ce que la substance sémiochimique est une phéromone d'insecte. 9. Method according to one of claims 1 to 8, characterized in that the semiochemical substance is an insect pheromone.
10. Méthode selon la revendication 9, caractérisée en ce que l'étape d.) de diffusion de ladite substance sémiochimique depuis la composition solide imprégnée est réalisée dans une parcelle agricole et que la méthode permet de protéger ladite parcelle contre les insectes ravageurs. 10. Method according to claim 9, characterized in that step d.) of diffusion of said semiochemical substance from the impregnated solid composition is carried out in an agricultural plot and that the method makes it possible to protect said plot against insect pests.
11. Méthode selon la revendication 10, caractérisée en ce que la composition solide est solidaire d'un support. 11. Method according to claim 10, characterized in that the solid composition is integral with a support.
12. Méthode selon la revendication 11, caractérisée en ce que le support comprend un article choisi dans le groupe comprenant un piquet, un tuteur, une clôture, une palissade, une agrafe et un crochet. 12. Method according to claim 11, characterized in that the support comprises an article chosen from the group comprising a stake, a stake, a fence, a palisade, a staple and a hook.
13. Méthode selon la revendication 11, caractérisée en ce que le support comprend un article choisi dans le groupe comprenant plaque en carton, plaque en verre, plaque en plastique, plaque métallique, chiffon, bâche, t-shirt ou tissu. 13. Method according to claim 11, characterized in that the support comprises an article chosen from the group comprising cardboard plate, glass plate, plastic plate, metal plate, cloth, tarpaulin, t-shirt or fabric.
14. Composition liquide comprenant au moins une résine polymérique, au moins un solvant, optionnellement au moins un pigment, optionnellement au moins une charge, optionnellement au moins une substance sémiochimique et au moins un copolymère à blocs acryliques, ledit copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle, caractérisée en ce que la résine polymérique est choisie dans le groupe comprenant les résines cellulosiques, les résines vinyliques et les résines polyuréthanes, mono ou bicomposants. 14. Liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, optionally at least one semiochemical substance and at least one acrylic block copolymer, said acrylic block copolymer comprising at least at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, characterized in that the polymeric resin is chosen from the group comprising cellulosic resins, vinyl resins and polyurethane resins, one- or two-component.
15. Composition selon la revendication 14, caractérisé en ce que ladite composition est durcie ou solidifiée et que la résine polymérique constitue une phase continue dans laquelle est dispersé et immobilisé le au moins un copolymère à blocs acryliques comprenant au moins un bloc polyméthacrylate d'alkyle et au moins un bloc polyacrylate d'alkyle, la charge optionnelle et le pigment optionnel. 15. Composition according to Claim 14, characterized in that the said composition is hardened or solidified and that the polymeric resin constitutes a continuous phase in which is dispersed and immobilized the at least one acrylic block copolymer comprising at least at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block, the optional filler and the optional pigment.
16. Article comprenant une composition solide selon la revendication 15. 16. Article comprising a solid composition according to claim 15.
17. Article selon la revendication 16, caractérisé en ce que la surface de l'article est revêtu en totalité ou en partie par la composition solide. 17. Article according to claim 16, characterized in that the surface of the article is coated in whole or in part with the solid composition.
18. Article selon la revendication 16 ou 17, caractérisée en ce qu'il est en en verre, textile, papier, carton, plastique, brique, cuir, bois, fibres végétales, métal ou céramique. 18. Article according to claim 16 or 17, characterized in that it is made of glass, textile, paper, cardboard, plastic, brick, leather, wood, plant fibers, metal or ceramic.
19. Article selon les revendications 16 à 18, caractérisé en ce qu'il se présente sous la forme d'un piquet, tuteur, clôture, palissade, agrafe, crochet, plaque en carton, plaque en verre, plaque en plastique, plaque métallique, chiffon, bâche ou t-shirt. 19. Article according to claims 16 to 18, characterized in that it is in the form of a post, tutor, fence, palisade, staple, hook, cardboard plate, glass plate, plastic plate, metal plate , rag, tarp or t-shirt.
20. Utilisation d'une composition selon la revendication 14 ou 15 pour la diffusion de ladite susbtance sémiochimique. 20. Use of a composition according to claim 14 or 15 for the diffusion of said semiochemical substance.
21. Utilisation d'une composition selon la revendication 15 pour l'absorption et la diffusion d'une substance sémiochimique. 21. Use of a composition according to claim 15 for the absorption and diffusion of a semiochemical substance.
PCT/FR2021/051588 2020-09-17 2021-09-16 Surface-coating fluid composition for absorbing and diffusing volatile compounds WO2022058689A1 (en)

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FRFR2009431 2020-09-17
FR2009431A FR3114100B1 (en) 2020-09-17 2020-09-17 FLUID COMPOSITION FOR SURFACE COATING FOR ABSORPTION AND DIFFUSION OF VOLATILE COMPOUNDS

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