Self-adhesive, multi-layered device impregnated with a semiochemical substance

Abstract

The present invention relates to a self-adhesive multilayer device comprising successively: a first adhesive layer; a support layer; a second adhesive layer; an active layer comprising a block copolymer and optionally a semiochemical substance, said block copolymer being an acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, a styrenic block copolymer comprising at least one polystyrene block and at least one polydiene block possibly hydrogenated, or a mixture thereof.The present invention also relates to a kit comprising one or more self-adhesive multi-layer devices and a composition comprising a semiochemical substance; as well as the use of this device or kit in a method of diffusing a semiochemical substance and for the protection of a plant or stored goods against harmful animals such as insects or mammals including rodents.

Description

Title of the invention: Self-adhesive multi-layer device impregnated with a semiochemical substance TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to a self-adhesive, multi-layered device that can be impregnated and recharged with a semiochemical substance and allows for the diffusion of this semiochemical substance over time. The present invention also relates to a kit comprising one or more self-adhesive, multi-layered devices and a composition comprising a semiochemical substance. The present invention further relates to the use of this device or kit in a method of diffusing a semiochemical substance and for protecting plants or stored foodstuffs against pests such as insects or mammals such as rodents. STATE OF PRIOR ART

[0002] Semiochemical substances (pheromones, kairomones, allomones and synomones) are volatile substances increasingly used in many fields, for example, to control animal behavior or to regulate pest insect populations.

[0003] These semiochemical substances are chemically sensitive molecules, particularly sensitive to oxidation (especially in the presence of UV radiation or free radicals) or to temperature changes, because they contain unsaturated chemical bonds (double or triple bonds), alcohol groups, or stretched ether rings. However, the formation of impurities through oxidation processes can have catastrophic effects on the effectiveness of semiochemicals (for example, an attractant can become a repellent, or the pheromone of one particular insect can be transformed into the pheromone of another insect).

[0004] Furthermore, semiochemical substances are generally composed of a mixture of organic molecules. Each molecule has its own volatility, and volatilities can therefore vary considerably depending on the nature of the molecule. For the effect of the mixture to be optimal, each of the constituent molecules must be diffused in a controlled and balanced manner.

[0005] One of the major problems that arises in order to optimally use these semiochemical substances is therefore the possibility of storing and releasing them using materials that not only preserve the purity of the semiochemical substances during the manufacture of the device and during the time of use, but also allow controlled release at sufficient rates over long periods periods. Another problem is being able to load materials multiple times to avoid having to craft and use a new item each time a new use is desired.

[0006] This diffusion can be done, among other things, by means of wicks immersed in a reservoir bottle, but this device has the disadvantage of being bulky and costly in materials (plastic bottle, solid non-recyclable wick).

[0007] Another diffusion method can be achieved by simply spraying the semiochemical substances onto a substrate. In this case, the user faces several distinct technical problems. The first problem is slowing down and controlling the diffusion of the semiochemical substances over time. The second problem is the formation of an unsightly greasy stain at the spray application site. The third problem is protecting the deposit from being unintentionally wiped away by contact with an object or fabric.

[0008] To solve this set of technical problems, it is necessary to develop a compact diffuser for semiochemical substances, for example in the form of a thin film, applicable to any type of surface, curved or flat. This diffuser must allow both the formation of a compact reservoir of semiochemical substances with a minimal volume and a large diffusion surface. It must allow for controlled diffusion of the semiochemical substances over time to extend the duration of effectiveness to 6 to 10 days, and absorb the semiochemical substances sufficiently quickly (on the order of a few minutes) so as to protect them from accidental wiping by contact with another surface and to allow for recharging with semiochemical substances. Advantageously, this compact diffuser will have an aesthetically pleasing surface that is not altered by the deposition of the semiochemical substances.

[0009] The use of polymeric matrices for the release of active substances, particularly semiochemical substances, has been known for a long time, having already been mentioned, for example, in Campion's review (DG Campion, Pestic. Sci. 1978, 9, 434-440). This publication specifically refers to the use of rubbery (or elastomeric) matrices. However, it also emphasizes that such matrices do not allow for continuous release over time and are highly sensitive to atmospheric conditions.

[0010] Later, other elastomeric matrices were proposed, for example, in 1987, in US patent 4,703,070. However, these elastomeric matrices require the incorporation of the active substance before the elastomeric matrix is ​​fully crosslinked. Because of their specific chemical structures (unsaturated bonds, presence of alcohol functions, etc.), few semiochemical substances can withstand, without deterioration, either the high temperatures required for the completion of crosslinking or the reactive components of the prepolymer. Furthermore, the activity of semio- chemical behavior is strongly influenced by even a slight deterioration of the molecule (such as a change in isomerism, for example).

[0011] Another thermoplastic matrix for the release of semiochemicals was described in 1996 in US patent 5,504,142. In this case, the matrix is ​​a Pebax®-type copolymer. Pebax® is a thermoplastic elastomer or a plasticizer-free flexible polyamide composed of a regular linear chain of rigid polyamide segments and flexible polyether segments. However, this type of matrix requires the use of an undecylenic acid-type solvent as a carrier for the active substance to penetrate the copolymer matrix. This solvent (derived from undecylenic acid, whose biocidal properties are well known to those skilled in the art) necessary for carrying out the process described in this invention is potentially harmful to the environment or may have a negative interaction with animals. The presence of such solvents is therefore a prohibitive factor for the use of such a matrix to store and release semiochemical substances.

[0012] Another family of copolymer matrices was subsequently 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 high storage capacity for this molecule, such a copolymer led to very short release times of the active substance, which is incompatible with the long release times required for the use of semiochemicals in agriculture. In 2010, Shakil et al. (p.228 of the review by Kah and Hofmann in Environment International 2014, 63, 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 semiochemical substances.

[0013] Ethylene and vinyl acetate copolymer-based matrices have also been tested to deliver bioactive compounds such as food attractants and pesticides, as described in US patent 5,135,744. However, the mixing of the copolymer and the bioactive compound and the final shaping (extrusion) must be done at high temperatures (between 80°C and 110°C), which is not feasible with most semiochemical substances, which either do not withstand these transformation conditions or evaporate rapidly at the extruder outlet, making the semiochemical substance load in the plastic difficult to control.

[0014] Other copolymers have also been proposed, for example in WO2012 / 095444 which describes the formation of microcapsules composed of several polymers including Cl-C24-alkyl esters of acrylic acid. This type of matrix can only be used for Semiochemical substances that are not sensitive to the peroxides necessary for matrix polymerization—that is, for a limited number of semiochemical substances. Similarly, international application WO2013 / 156249 describes a composition comprising a pesticide and a statistical copolymer resulting from the copolymerization of acrylic and / or methacrylic acid (monomer A), poly(C2-C6 alkylene glycol) (mono-Ci2-C22-alkyl) (meth)acrylate (monomer B), and Ci-C8-alkyl (meth)acrylate (monomer C). However, this type of statistical copolymer is once again obtained by polymerization with a radical generator (in the examples of this patent, tert-butylperpivalate), which, as previously emphasized, poses a risk of degradation of the semiochemical substances.For example, it is well known that (E,Z)-7,9 dodecadienylacetate (the sex pheromone of the European grapevine moth) is transformed under these conditions into (E,E)-7,9 dodecadienylacetate which has no effect on the insect.

[0015] Similarly, 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 that can be sufficiently softened at a temperature between 45°C and 160°C to incorporate the substances. The matrix is ​​formed of a substantially linear sequenced copolymer that 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 comprise 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 incompatible with pheromones. Furthermore, once the pheromone has been diffused, it is not possible to recharge the matrix.

[0016] International application WO01 / 50859 also describes a slow-release insect repellent composition comprising an insect repellent, an oleophilic chemical soluble in the insect repellent, and a polysaccharide-type matrix in which the combination of the insect repellent and the oleophilic chemical is trapped within the matrix such that the insect repellent is slowly released from the matrix. The problem with this type of composition is that solidification involves a drying step at temperatures incompatible with semiochemicals that are highly sensitive to heat and will evaporate during this step. Furthermore, once the insect repellent compound has completely diffused, the composition cannot be recharged.

[0017] EP3187046 describes the use of block copolymers as a support material for To diffuse pheromones, block copolymers are used in the form of solid particles or millimeter-sized granules. Since diffusion distance plays a primary role in diffusion kinetics, a person skilled in the art would not have used such a material in the form of a thin film, as they would have expected this that a drastic reduction in the thickness of the material induces a drastic acceleration of the diffusion of pheromones, so that the control of this diffusion is no longer mastered.

[0018] FR3032972 also describes a composition comprising an elastomeric phase A polymer in the form of a sequenced acrylic copolymer and an active odorant compound, allowing the release of said active odorant compound over a given period of time. This document describes, for example, articles obtained by injection molding, extrusion, co-extrusion, or extrusion / blow molding, leading to the preparation of profiled parts or elements, blocks, tubes, sheets, or films. However, it does not describe how to integrate such a film into a device for diffusing semiochemical substances.

[0019] There is therefore a need to develop a semiochemical diffusion device that is compact, rechargeable, and allows for the diffusion of semiochemical substances over periods ranging from 6 to 10 days. Summary of the invention

[0020] The present invention therefore relates to a self-adhesive multi-layered device comprising successively: 1. a first adhesive layer; 2. a support layer; 3. a second adhesive layer; 4. an active layer comprising a block copolymer and optionally a semiochemical substance, said block copolymer being an acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, a styrenic block copolymer comprising at least one polystyrene block and at least one polydiene block possibly hydrogenated, or a mixture thereof.

[0021] The device according to the present invention is a device for diffusing a semiochemical substance (e.g., C4 to C18 compounds possessing alcohol, ketone, aldehyde, ester, alkene, alkyne, aromatic, etc. functions), positionable on many surfaces.

[0022] This is a multilayer device comprising a thin polymeric film, obtained for example by extrusion, superimposed on a support structure itself composed of several layers to give the whole the required mechanical strength, the adhesive character, and the desired aesthetic appearance.

[0023] This device, through the progressive release of a semiochemical substance, makes it possible to repel insects or mammals (e.g. rodents) that are pests of plants such as crops or stored goods.

[0024] The active layer of this device is a thin layer (e.g., a few hundred micrometers) that can be easily obtained by extrusion and can be easily impregnated with a semiochemical (e.g., by simply spraying the semiochemical substance, pure or mixed with other ingredients such as a solvent, onto the surface of this layer). Surprisingly, given its thinness, the active layer also allows for the efficient, controlled, and balanced release of this semiochemical substance, even when it is a mixture of active molecules, for example, in the case of a pheromone mixture. Indeed, despite the different volatilities of the molecules composing a pheromone mixture, the active layer makes it possible to balance the diffusion rates of these different molecules in order to obtain the desired pheromone activity.

[0025] Once the active substance has been diffused, the device according to the invention, by virtue of the nature of its active layer, can be easily recharged by applying the semiochemical substance to its surface, for example, by means of a spray. Recharging the active layer does not cause any detachment of this layer despite swelling due to the adsorption of the semiochemical substance. Thus, the active layer adheres well to the support layer via the second adhesive layer, even when it is loaded with the semiochemical substance.

[0026] The structure of the device according to the invention, in the form of a thin, self-adhesive, flexible, and non-brittle film, also allows it to conform to any type of surface, whether flat or curved. Furthermore, its external appearance is preserved over time (no whitening of the active layer, for example), thus maintaining the same aesthetic appeal.

[0027] The present invention also relates to a kit comprising one or more self-adhesive multilayer devices according to the invention and a composition comprising a semiochemical substance.

[0028] The present invention further relates to the use of a self-adhesive multilayer device according to the invention or a kit according to the invention for the diffusion of a semiochemical substance, in particular for the absorption and diffusion of a semiochemical substance.

[0029] The invention also relates to a method for diffusing a semiochemical substance comprising the following steps: a. application of a self-adhesive multi-layer device according to the invention onto a substrate, b. impregnation of the active layer of the self-adhesive multilayer device with a semiochemical substance by bringing the active layer into contact with the semiochemical substance, c. diffusion of the semiochemical substance from the active layer of the device multi-layer self-adhesive, d. optionally, repeating steps b) and c).

[0030] The present invention also relates to the use of a self-adhesive multi-layer device according to the invention or a kit according to the invention for the protection of a plant such as a crop or stored foodstuffs against harmful animals such as insects. DETAILED DESCRIPTION OF THE INVENTION Self-adhesive multi-layer device

[0031] As previously stated, the self-adhesive multi-layer device according to the invention comprises at least 4 layers, namely (1) a first adhesive layer; (2) a support layer; (3) a second adhesive layer; and (4) an active layer.

[0032] The first adhesive layer is intended to be glued onto a surface, while the second adhesive layer serves to adhere the active layer to the support layer.

[0033] The adhesive layers may be made of any suitable adhesive material (in particular to allow the device to be bonded to any type of substrate), such materials being well known to those skilled in the art. Thus, the adhesive layers will advantageously comprise, in particular be made of, an acrylic polymer.

[0034] The adhesive layers typically each have a thickness of 1 pm to 50 pm, in particular 2 pm to 20 pm, preferably 5 pm to 15 pm. Such a thickness can be measured by optical microscopy.

[0035] The first adhesive layer can also be protected by a protective layer. This protective layer will be removed before use, i.e., just before sticking the self-adhesive multi-layer device onto the chosen substrate.

[0036] The support layer will typically be a layer of cellulose, i.e. paper, or a metallic or plastic film.

[0037] It may optionally be printed on its side in contact with the second adhesive layer so as to form a design. The printing may be done using ink (e.g., screen printing ink). Thus, the device according to the invention may include a layer of ink, not uniformly distributed, between the support layer and the second adhesive layer.

[0038] The support layer typically has a thickness of 1 pm to 200 pm, in particular 5 pm to 150 pm, preferably 10 pm to 100 pm, for example about 50 pm. Such a thickness can be measured by optical microscopy.

[0039] The active layer is intended to be in contact with ambient air. It consists of a film with absorption and diffusion capabilities for semiochemical substances thanks to the microstructure of its material. Diffusion occurs slowly according to a kinetic profile adapted to the application. Once the semiochemical substance has diffused, the film can then be recharged with semiochemical substance by contacting the film with a composition containing the semiochemical substance.

[0040] This film is also flexible and deformable so that it can be positioned on non-planar surfaces and conform to the surface to which it is applied. Typically, the film material will have a tensile Young's modulus less than or equal to 1500 MPa (measured according to ISO 527) and an elongation at break greater than or equal to 20% (measured according to ISO 527).

[0041] Preferably, this film also has the property of being transparent so that the substrate layer to which it is applied can be seen through it. This makes it possible, in particular, to see any decoration printed on the substrate layer. Typically, the film material will have a haze of 20% or less (measured according to ISO 13468) and a light transmission (LT) of 80% or more (measured according to ISO 13468).

[0042] The active layer thus comprises a block copolymer and optionally a semiochemical substance, said block copolymer being an acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, a styrenic block copolymer comprising at least one polystyrene block and at least one polydiene block, possibly hydrogenated, or a mixture thereof. Preferably, the block copolymer is an acrylic block copolymer.

[0043] In the context of the invention, a "block copolymer," also called a "sequenced copolymer," is understood to be a copolymer containing, in particular consisting of, a linear sequence of several different blocks, each block being composed of a polymer chain, two adjacent blocks therefore being composed of different polymer chains. A block copolymer constitutes a single macromolecule, such that each block is covalently linked to the next block, either directly by a covalent bond or via a constituent unit that is not an integral part of the blocks. The polymer chain constituting a block will advantageously result from the polymerization of one or more, in particular 1 or 2, monomer species, preferably one monomer species.

[0044] By "alkyl", we mean a monovalent saturated hydrocarbon group, linear or branched. The alkyl group advantageously comprises 1 to 10 carbon atoms ((CrC io)alkyl), in particular 1 to 8 carbon atoms ((Ci-C8)alkyl), especially 1 to 6 carbon atoms ((Ci-C6)alkyl), preferably 1 to 4 carbon atoms ((C1-C4 ) alkyl).

[0045] By “diene” is meant a linear or branched hydrocarbon group, comprising two C=C double bonds, for example conjugated dienes (double bonds The diene can be composed of two or more single bonds, preferably conjugated (double bonds separated by a single bond), conjugated (double bonds on the same carbon atom), or non-conjugated (double bonds separated by two or more single bonds). The diene advantageously comprises 4 to 10 carbon atoms, particularly 4 to 8 carbon atoms, especially 4 to 6 carbon atoms, and preferably 4 or 5 carbon atoms. Examples include butadiene and isoprene.

[0046] The term "polydiene" refers to a polymer resulting from the polymerization of a diene.

[0047] The block copolymer is advantageously a two-block copolymer or a three-block copolymer, preferably a three-block copolymer. When the block copolymer is a three-block copolymer, it advantageously comprises at most two identical blocks, preferably two identical blocks, in particular two blocks of alkyl polymethacrylate or polystyrene.

[0048] When the block copolymer is an acrylic block copolymer, the block copolymer comprises at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block.

[0049] Alkyl polymethacrylate is advantageously methyl polymethacrylate (PMMA) and / or alkyl polyacrylate is advantageously butyl polyacrylate (PABu) or a copolymer of butyl acrylate and 2-ethylhexyl acrylate, preferably butyl polyacrylate (PABu).

[0050] The acrylic block copolymer is advantageously a two-block copolymer or a three-block copolymer, preferably a three-block copolymer. When the acrylic block copolymer is a three-block copolymer, it advantageously comprises at most two identical blocks, preferably two identical blocks, in particular two alkyl polymethacrylate blocks.

[0051] Advantageously, the acrylic block copolymer is a tri-block copolymer of the PMMA-PABu-PMMA type. It may be the Nanostrength® M53 copolymer.

[0052] When the block copolymer is a styrenic block copolymer, the block copolymer comprises at least one polystyrene block and at least one polydiene block, possibly hydrogenated.

[0053] The possibly hydrogenated polydiene may be polybutadiene, polyisoprene, polyethylene-butylene (resulting from the hydrogenation of polybutadiene), or polyethylene-propylene (resulting from the hydrogenation of polyisoprene).

[0054] The styrene block copolymer is advantageously a two-block copolymer or a three-block copolymer, preferably a three-block copolymer. When the styrene block copolymer is a three-block copolymer, it advantageously comprises at most two identical blocks, preferably two identical blocks, in particular two polystyrene blocks.

[0055] Advantageously, the styrenic block copolymer is a tri-block copolymer of type SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SEBS (styrene-(ethylene-butylene)-styrene), or SEPS (styrene-(ethylene-propylene)-styrene).

[0056] The active layer typically has a thickness of 5 pm to 500 pm, in particular 10 pm to 400 pm, especially 20 pm to 300 pm, for example 50 pm to 250 pm, preferably 100 pm to 250 pm, for example about 200 pm. Such a thickness can be measured by optical microscopy.

[0057] This active layer can be prepared by extrusion and calendering. This makes it possible to obtain a film of the required thickness.

[0058] The active layer may also include a semiochemical substance. If the active layer does not contain such a substance, it may subsequently be impregnated with such a semiochemical substance.

[0059] The active layer, particularly when impregnated with a semiochemical substance, may be protected by a protective layer, preferably waterproof, to be removed at the time of use, once the device has been bonded to the chosen substrate. This protective layer, preferably waterproof, may be made of any suitable material well known to those skilled in the art. For example, it may be an aluminized protective layer.

[0060] When present, the semiochemical substance will advantageously represent from 1% to 80%, in particular from 1% to 50%, in particular from 2% to 40%, more particularly from 5% to 30%, preferably from 5% to 20% by weight relative to the weight of the active layer.

[0061] The term "semiochemical substance" refers to a chemical substance emitted by a plant or animal into the environment and which has signal value between living beings. It may consist of a molecule or a mixture of molecules.

[0062] Semiochemical substances are classified into: • pheromones that allow communication between individuals of the same species, and • allomones, kairomones and synomones which are exchanged between animals or plants belonging to different species.

[0063] In the context of the present invention, the semiochemical substance will more particularly be an insect pheromone.

[0064] Semiochemical substances can be perceived by different organs. Thus, semiochemical substances can be perceived by smell for volatile compounds, or by taste for non-volatile compounds. The information carried by semiochemical substances can allow, for example, the location and recognition of a sexual partner.

[0065] Semiochemical substances, and more particularly pheromones, are chemical compounds, a large number of examples of which (8000) are given in the online database Pherobase (www.pherobase.com).

[0066] According to one embodiment of the invention, the semiochemical substance is a fatty-chain semiochemical substance, and is advantageously chosen from the group of pheromones, in particular insect pheromones. More particularly, it will be a volatile substance.

[0067] The term "volatile" refers to the ability of the semiochemical substance to change from a liquid to a gaseous state under ambient pressure and temperature conditions, i.e., at approximately 20°C and atmospheric pressure (1013.25 hPa). A "volatile" liquid is a liquid whose saturated vapor pressure at 20°C is greater than 1 Pa, preferably between 1 Pa and 3000 Pa, particularly between 1 Pa and 2500 Pa, more preferably between 1 Pa and 1500 Pa, more preferably between 1 Pa and 1000 Pa, and in particular between 1 Pa and 700 Pa.

[0068] For the purposes of this invention, "fat chain" means an aliphatic hydrocarbon chain, preferably linear or branched, saturated or unsaturated, comprising 5 to 24, in particular 5 to 18, preferably 6 to 16, carbon atoms.

[0069] The semiochemical substance according to the invention shall advantageously be chosen from among alkanols and alkenols having from 5 to 18 carbon atoms, alkanals and alkenals having from 5 to 18 carbon atoms, alkanones having from 6 to 18 carbon atoms, alkyl or alkene acetates having from 5 to 18 carbon atoms, 1,7-dioxaspirononane, 3- or 4-hydroxy-1,7-dioxaspirononane, benzyl alcohol, Z-(9)-tricosene (muscalure), heneicosan, diacetyl, alkanoic acids having from 5 to 16 carbon atoms (e.g., caprylic acid, lauryl acid), pinene, methyleugenol, eugenol, the 4-Methoxy-Cinnamaldehyde, estragole, indole, ethyldodecanoate, tert-butyl 4-chloro-2-ethylcyclohexane-carboxylate, tert-butyl 5-chloro-2-ethylcyclohexane-carboxylate, mycrenone, cucurbitacin, trimedlide, (E,E)-8,10-dodecadien-l-ol (codelmone) and mixtures thereof.

[0070] Advantageously, the semiochemical substance can be chosen from iron-rugineol, ferrugineone or a mixture of ferrugineol-ferrugineone.

[0071] 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, E-11-tridecenyl 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-tridecadienyl acetate, [beta]-ionone, 8-Methyl-2-Decyl Propanoate, E,E-9,II-Tetradecadienyl Acetate, Z,Z-9,12-Tetradecadienyl Acetate, Z,Z-7,II-Hexadecadienyl Acetate, E,Z-7,II-Hexadecadienyl Acetate, Z,E-7,II-Hexadecadienyl Acetate, E,E-7,II-Hexadecadienyl Acetate, Z,Z-II,13-Hexadecadienyl Acetate, E,Z-II,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, 4methyl 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,ll-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-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol, Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecenol, (Z)-14-methyl-8-hexadecenol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecanal, tetradecanal, Z-7-tetradecanal,Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, 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-11-hexadecenal, E1-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)-14-methyl-8-hexadecenal, Z,Z-7,11-hexadecadienal, the 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, (+)-cis-7,8-epoxy-2-methyloctadecane (disparlure), 3-methyl-2-cyclohexen-l-ol (seudenol), 6-methyl-5-hepten-2-ol (sulcatol), 2-methyl-6-methylene-7-octen-4-ol (ipsenol), the , 2-Methyl-6-methylene-2,7-octadien-4-ol (ipsdienol), cis-2-isopropenyl-1-methylcyclobutane-ethanol (size I), Z-3,3-dimethyl-1-cyclohexane-ethanol (size II), Z-3,3-dimethyl-1-cyclohexane-acetaldehyde (size III), E-3,3-dimethyl-1-cyclohexane-acetaldehyde (size IV), cis-4,6,6-trimethylbicyclo[3,l,l]hept-3-en-2-ol (cis-2-verbenol), 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, 2,6,6-trimethylbicyclo[3,l,l]hepten-2-ene ([alpha]-pinene), 4,ll,ll-trimethyl-8-methylene-bicyclo[7,2,0]undecane ([alpha]-caryophyllene), Z-9-tricosene (muscalure), 1'[alpha]-multistriatine, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,l,0]nonane (lineatine), 2-ethyl-l,6-dioxaspiro[4,4]nonane (chalcogran), l,5-dimethyl-6,8-dioxabicyclo[3,2,l]octane (frontaline), rendo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,l]octane (endo-brevicomine),rexo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,l]octane (exo-brevicomine), (Z)-5-(l-decenyl)dihydro-2-(3H)-furanone, 3,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol (famesol), 3,7,1l-trimethyl-l,6,10-dodecatrien-3-ol (nerolidol), 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-methylethenyl)-5,8-decadien-l-ol acetate, the 3-methylene-7-methyl-octen-l-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-l-ol propionate, or (Z)-3,9-dimethyl-6-(l-methyl-ethenyl)-3,9-decadien-l-ol. The semiochemical substance may be any one of these fatty-chain pheromones or a mixture thereof.

[0072] According to one embodiment, the semiochemical substance is chosen from the group of pheromones, in particular insect sex pheromones, in particular oil-chain insect sex pheromones, and more particularly from the group consisting of pheromones of pine processionary moths, oak processionary moths, box tree moths, silkworms, codling moths, peach fruit fly, corn borer, European grapevine moth, amphipods, cacao mite pheromones, palm or banana weevils, and pheromones of the Cochylis of the vine, as well as their mixtures.

[0073] In a particular embodiment of the invention, the semiochemical substance may be protected against the action of light and / or oxygen, in particular by the use of antioxidants and / or anti-UV agents. Thus, the active layer may also contain at least one additive chosen from antioxidant agents, anti-UV agents and their mixtures.

[0074] Antioxidant agents may be selected from the group consisting of vitamin E, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and mixtures thereof. These antioxidants protect the semiochemical substance from degradation by oxygen and may be added in amounts ranging from 0.1% to 3%, particularly between 0.5% and 2% by weight relative to the weight of the active layer.

[0075] The UV-blocking agents may be selected from the group consisting of beta-carotene, p-aminobenzoic acid, hindered amines, and hindered alkoxyamines and mixtures thereof. The hindered amines may be derivatives of 4-tetramethylpiperidine, notably known as HALS (hindered amine light stabilizers) and described in Schaller, C., Rogez, D. & Braig, A. "Hindered amine light stabilizers in pigmented coatings." J Coat Technol Res 6, 81-88 (2009). The hindered alkoxyamines may be, for example, Solvay's TEMPO. These anti-UV agents protect semiochemicals from degradation by light and can be added in quantities ranging from 0.1% to 3%, particularly between 0.5% and 2% by weight relative to the weight of the active layer.

[0076] The self-adhesive multi-layer device according to the invention can have any size and any shape, depending on the intended application. Kit

[0077] The kit according to the invention comprises one or more self-adhesive multilayer devices according to the invention and a composition, preferably liquid, comprising a semiochemical substance.

[0078] According to one embodiment, the self-adhesive multilayer devices according to the invention do not include any semiochemical substance.

[0079] The active layer of these devices will advantageously be impregnated with a semiochemical substance using the composition included in the kit. This impregnation can be carried out, for example, by spraying, by brushing or roller application, or by immersion, preferably by spraying, preferably once the device has been glued to the chosen substrate.

[0080] The composition, preferably liquid, advantageously comprises, in particular, a semiochemical substance, optionally solubilized in a solvent. The solvent may be, in particular, an ether such as di(propylene glycol) methyl ether, an alcohol such as isopropanol, etc. Preferably, the composition does not contain a solvent.

[0081] The composition may also include one or more antioxidants and one or more anti-UV agents as defined above in order to protect the semiochemical substance against the action of UV and / or oxygen.

[0082] Additives such as stabilizers, preservatives or rheology agents may possibly be present in the composition.

[0083] The composition will preferably be contained in a container that allows it to be sprayed. It may also be contained in a container equipped with a drip system or a brush. Dissemination method

[0084] The self-adhesive multilayer device according to the invention and the kit according to the invention are useful for the diffusion of a semiochemical substance, in particular according to a method comprising:

[0085] a) the application of a self-adhesive multi-layer device according to the invention onto a substrate,

[0086] b) impregnation of the active layer of the self-adhesive multilayer device with a semiochemical substance by bringing the active layer into contact with the semiochemical substance,

[0087] c) the diffusion of the semiochemical substance from the active layer of the self-adhesive multilayer device,

[0088] d) optionally, repeating steps b) and c).

[0089] Step a) may be carried out before or after step b). Step a):

[0090] The self-adhesive multi-layer device according to the invention can be applied to any type of support, whether flat or curved, since its flexible structure allows the device to conform to the shape of the support, and regardless of the material of the support.

[0091] Thus, the support can be made of a material chosen from the group consisting of glass, textile, paper, cardboard, plastic, brick, concrete, wood, leather, vegetable fibers, metal, ceramic, and a combination thereof.

[0092] A support may include 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, a glazed surface such as a window, or a piece of furniture, for example a cupboard.

[0093] A support may also include an article, that is to say a discreet or individualized object. This article may be in the form of a stake, a support, a fence, a palisade, a staple, a hook, a cardboard plate, a glass plate, a plastic plate, a metal plate, a cloth, a tarpaulin, a bag, a T-shirt, etc. Step b):

[0094] The impregnation of the active layer can be achieved by simply bringing the active layer into contact with a composition, preferably liquid, comprising or consisting of the semiochemical substance, such as the composition of the kit according to the present invention.

[0095] Thus, the composition, preferably liquid, will advantageously comprise, in particular consist of, a semiochemical substance, optionally solubilized in a solvent. Additives such as stabilizers, preservatives, or rheological agents may optionally be present in the composition. The solvent may be, in particular, an ether such as di(propylene glycol) methyl ether, an alcohol such as isopropanol, etc. Preferably, the composition does not contain a solvent.

[0096] Such contact can be achieved for example by spraying the composition onto the active layer, by brushing or rolling the active layer with the composition, or by soaking the active layer in the composition.

[0097] Given the prices of semiochemical substances, an application that limits losses will be preferred, such as application by spraying. Step c):

[0098] Once the active layer is impregnated with the semiochemical substance, the semiochemical substance will be able to diffuse progressively through this active layer and provide protection in its immediate environment against harmful animals such as insects or mammals including rodents.

[0099] This diffusion will advantageously be spread over a period of 6 to 10 days. Step d):

[0100] An advantage of the device according to the invention is its ability to be recharged with semiochemical substance, which makes it possible to repeat steps b) and c) one or more times.

[0101] Thus, once the initial quantity of semiochemical substance present in the active layer has been diffused, the active layer of the device according to the invention can be re-impregnated with a semiochemical substance according to the conditions of step b). Use

[0102] The present invention also relates to the use of a self-adhesive multi-layer device according to the invention or a kit according to the invention for the protection of a plant (e.g. a crop) or stored foodstuffs against harmful animals such as insects.

[0103] Pheromones will make it possible to influence the behavior of animals such as insects (e.g., Lepidoptera), rodents, or even wild animals such as... Game animals (e.g., roe deer, red deer, fallow deer, wild boar) are responsible for damage to plants (especially crops) and stored goods. The pheromone(s) will be chosen according to the animal (e.g., insect or mammal such as a rodent) against which the plant or stored goods wish to be protected. For example, the pheromone could be chosen to lure a lepidopteran using a trapping protocol or a mating disruption protocol.

[0104] Preferably, the plants to be protected are vines, field crops (rice, corn, cotton, soybeans, sunflowers, etc.), vegetable crops (tomatoes, salads, peppers, melons, cucumbers, cabbages, spinach, etc.), trees (e.g. fruit or ornamental trees (apple trees, peach trees, pear trees, citrus trees, almond trees, etc.), forests (pine forests, oak forests, etc.)), or shrubs (boxwood, etc.).

[0105] The stored goods to be protected may be crops such as grains (e.g. wheat, corn, etc.) which should be protected during storage (e.g. in a grain loft) or goods stored in a dwelling, for example in a kitchen or a pantry.

[0106] In the context of the present invention, harmful animals are more particularly insects (for example the pine processionary moth, the oak processionary moth, the box tree moth, the silkworm, the codling moth, the peach tree fly, the corn borer, the European grapevine moth, the amphipod moth, the cocoa tree mirid moth, the palm or banana weevil, the grapevine cochylis) or even rodents.

[0107] The present invention is illustrated by the non-limiting examples below. EXAMPLES

[0108] Example 1: Absorption property as a function of the nature of the impregnation material used

[0109] The materials tested are injected in the form of 5A tensile test specimens (ISO 3167). The specimens are weighed and then contacted with methyl laurate by immersion in a methyl laurate bath at a temperature of 20°C. The specimens are retrieved after one hour, drained, and quickly washed on the surface with ethanol, then air-dried and weighed. The difference in weight observed compared to the initial mass of the specimen represents the amount impregnated. The specimens are then placed in a diffusion oven at 30°C. The results are presented in Table 1 below.

[0110] [Tables 1] Specimen material M53* PRnew* PMV* PU* ​​Quantity impregnated (mg) on ​​Ih 2295 1180 61 14 Percentage of impregnation 70% 40% 2% 0.5% Quantity (mg) diffused in study at 30°C 4 days 812 (35%) 964 (82%) 57 (93%) 8 (57%) 6 days 1282 (56%) 1074 (91%) 59 (96%) 12 (85%) 10 days 1698 (73%) 1176 (99%) 60 (98%) 13 (92%) 12 days 1864 (81%) 1180 (100%) 61 (100%) 14 (100%)

[0111] * M53 = Nanostrength® M53; PRNEW = Pebax® Rnew; PMV = Pebax® MV (polyether block amide); PU = polyurethane

[0112] The results show that a variation in the microstructure or the nature of the monomers can drastically change the absorption and diffusion properties. Nanostrength® M53 (acrylic block copolymer according to the invention) thus exhibits a high adsorption (impregnation) capacity associated with a sufficiently long and controlled diffusion of methyl laurate (semiochemical substance) over time (retention capacity).

[0113] Example 2: Physical measurement on test specimens 5a in raw material and in material impregnated with methyl laurate

[0114] Tensile test specimens 5A are tested on tensile test benches or on a durometer. They may or may not have been previously impregnated with methyl laurate (LM) according to the method described in Example 1. The degree of impregnation is modulated by leaving the specimens in the methyl laurate solution for a longer or shorter time.

[0115] The Young's modulus, elongation at break, and Shore hardness are then measured according to ISO 527 for Young's modulus and elongation at break, and according to ISO 868 for Shore hardness. The results obtained are presented in Table 2 below.

[0116] [Tables2] Specimen Young's Modulus (MPa) Elongation at break (%) Shore hardness (Shore degrees from 0 to 100) M53 157 30 37 M53 impregnated with 5% LM 143 43 32 M53 impregnated with 12% LM 48 48 22

[0117] The results show that Nanostrength® M53 meets the flexibility criteria required by the application regardless of the impregnation rate. Example 3: Impact of material thickness

[0118] The objective of this test is to demonstrate the importance of choosing the thickness of the active layer. To this end, two Nanostrength® M53 objects of different thicknesses were impregnated with a defined quantity of methyl laurate (LM) at room temperature by depositing the methyl laurate onto the surface to be impregnated.

[0119] The first object is a self-adhesive, multi-layered device according to the invention, measuring 5x5 cm2, comprising:

[0120] - a first adhesive layer of acrylic polymer of approximately 1 Opm;

[0121] - a layer of paper (cellulose) of approximately 50pm screen-printed with an ink;

[0122] - a second adhesive layer of acrylic polymer of approximately 1 Opm;

[0123] - a Nanostrength® M53 polymer film of approximately 200pm.

[0124] The second object is a Nanostrength® M53 plate of 5 x 5 cm2 with a thickness of 5 mm.

[0125] In both cases, the impregnation yield is greater than 99%.

[0126] The two objects were placed in diffusion at room temperature. The results obtained are presented in Table 3 below.

[0127] [Tables3] Device according to the invention (5x5 cm²) Plate (5x5 cm²) Thickness* 0.2 mm 5 mm Quantity of LM impregnated 126 mg 130 mg Time Residual LM mass (mg) Diffused LM mass (%) Average instantaneous diffusion rate (mg / h) Residual LM mass (mg) Diffused LM mass (%) Average instantaneous diffusion rate (mg / h) 1.5 h 121 5 3.7 114 12 10.6 18 h 90 29 1.9 85 35 1.7 96 h 25 80 0.8 45 65 0.5 120 h 18 86 0.3 40 69 0.2 144 h 15 88 0.1 35 73 0.2

[0128] * of Nanostrength® M53 material intended to be impregnated with methyl laurate

[0129] The results show that the device according to the invention diffuses more with a The residual quantity of methyl laurate was 11% after 144 hours, while the thicker material showed more than 25% residual methyl laurate. Furthermore, the device according to the invention demonstrates better control of diffusion during the first few hours of diffusion.

[0130] Finally, the diffusion yield over a given period, 6 days in the example, is better for the device according to the invention with 88.2% of methyl laurate diffused against only 73.2% for the thick material.

[0131] Thus, it is surprisingly observed that a more constant diffusion over time is obtained when the material is in the form of a thin film compared to a thick plate. The diffusion rate is lower at short times and higher at long times, which ensures a more regular instantaneous dose emitted over time for a thin diffusion system compared to a thick diffusion system. Example 4: Liquid composition of semiochemical

[0132] Several types of formulation can be considered for recharging the self-adhesive multilayer device according to the invention: • Formulation A: semiochemical substance solubilized in a penetrating organic solvent; • Formulation B: semiochemical substance solubilized in a non-penetrating organic solvent; • Formulation C: pure semiochemical substance.

[0133] Formulation A facilitates the penetration of the semiochemical substance into the active layer material. Formulation B eliminates the need for a solvent since only the semiochemical substance penetrates the active layer material, as does formulation C.

[0134] Example of formulation A:

[0135] In a 50 mL bottle fitted with a spray head are mixed (in %w / w): lauric acid (2%), oleic acid (2%) and di(propylene glycol) methyl ether (96%).

[0136] The mixture is homogenized. The mixture is then sprayed onto a device according to the invention at a distance of 5 cm. The impregnation rate observed after 30 min is 99% of the mixture.

[0137] Example of formulation B:

[0138] In a 50 mL bottle fitted with a spray head are mixed (in %w / w): methyl laurate (2%), methyl oleate (2%) and isopropanol (96%).

[0139] The mixture is homogenized. The mixture is then sprayed onto a device according to the invention at a distance of 5 cm. The observed impregnation rate is 3.7% of the mixture with an impregnation yield of the 2 active ingredients of 92%.

[0140] Example of formulation C:

[0141] A mixture of 20 / 80 (w / w) methyl laurate and methyl oleate is introduced into a bottle fitted with a dropper device.

[0142] 5 drops of the mixture are deposited onto the device according to the invention. The rate The measured impregnation rate after 30 minutes is 97%.

Claims

Claims

1. A self-adhesive multi-layer device successively comprising: (1) a first adhesive layer; (2) a support layer; (3) a second adhesive layer; (4) an active layer having a thickness of 5 μm to 500 μm and comprising a block copolymer and optionally a semiochemical substance, said block copolymer being an acrylic block copolymer comprising at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block.

2. Self-adhesive multi-layer device according to claim 1, characterized in that the block copolymer is a bi-block copolymer or a tri-block copolymer.

3. Self-adhesive multilayer device according to claim 2, characterized in that the tri-block copolymer comprises at most 2 identical blocks.

4. Self-adhesive multi-layer device according to any one of claims 1 to 3, characterized in that the polyalkyl methacrylate is polymethyl methacrylate (PMMA) and / or the polyalkyl acrylate is chosen from the group consisting of polybutyl acrylate (PABu) and a copolymer of butyl acrylate and 2-ethylhexyl acrylate.

5. Self-adhesive multilayer device according to any one of claims 1 to 4, characterized in that the acrylic block copolymer is a tri-block copolymer of the PMMA-PABu-PMMA type.

6. Self-adhesive multi-layer device according to any one of claims 1 to 5, characterized in that the semiochemical substance is an insect pheromone.

7. Self-adhesive multi-layer device according to any one of claims 1 to 6, characterized in that the active layer has a thickness of 10 pm to 400 pm, in particular of 20 pm to 300 pm, for example of 50 pm to 250 pm, preferably of 100 pm to 250 pm, for example of approximately 200 pm.

8. Self-adhesive multi-layer device according to any one of claims 1 to 7, characterized in that the first adhesive layer and the second adhesive layer each comprise an acrylic polymer, and advantageously have a thickness of 1 pm to 50 pm, in particular of 2 pm to 20 pm, preferably of 5 pm to 15 pm.

9. A self-adhesive multi-layer device according to any one of the claims- indications 1 to 8, characterized in that the first adhesive layer and / or the active layer is protected by a protective layer intended to be removed before use.

10. Self-adhesive multi-layer device according to any one of claims 1 to 9, characterized in that the support layer is made of cellulose, and advantageously has a thickness of 1 pm to 200 pm, in particular of 5 pm to 150 pm, preferably of 10 pm to 100 pm.

11. Self-adhesive multi-layer device according to any one of claims 1 to 10, characterized in that the support layer is printed on its face in contact with the second adhesive layer, in particular using an ink.

12. A kit comprising one or more self-adhesive multi-layer devices according to any one of claims 1 to 11 and a composition comprising a semiochemical substance.

13. A method for diffusing a semiochemical substance comprising the following steps: a) applying a self-adhesive multilayer device according to any one of claims 1 to 11 to a support, b) impregnating the active layer of the self-adhesive multilayer device with a semiochemical substance by bringing the active layer into contact with the semiochemical substance, c) diffusing the semiochemical substance from the active layer of the self-adhesive multilayer device, d) optionally, repeating steps b) and c).

14. Method according to claim 13, characterized in that the support is made of a material chosen from the group consisting of glass, textile, paper, cardboard, plastic, brick, concrete, wood, leather, vegetable fibers, metal, ceramic, and a combination thereof.

15. Method according to claim 13 or 14, characterized in that the support is a wall, opaque or transparent, such as a wall, a floor or a window, a piece of furniture, a stake, a stake, a fence, a palisade, a staple, a hook, a cardboard plate, a glass plate, a plastic plate, a metal plate, a cloth, a tarpaulin, a bag or a T-shirt.

16. Use of a self-adhesive multi-layer device according to any one of claims 1 to 11 or a kit according to claim 12 for the protection of a plant or stored goods against harmful animals such as insects or mammals, including rodents.