Self-adhesive multi-layer 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 polyalkylmethacrylate block and at least one polyalkylacrylate block, a styrene block copolymer comprising at least one polystyrene block and at least one optionally hydrogenated polydiene block, or a mixture thereof. The present invention also relates to a kit comprising one or more self-adhesive multilayer devices and a composition comprising a semiochemical substance; as well as the use of this device or kit in a method for diffusing a semiochemical substance and for modifying behavior in an animal.

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-layer device capable of being impregnated and recharged with a semiochemical substance and allowing the diffusion over time of this semiochemical substance. The present invention also relates to a kit comprising one or more self-adhesive multi-layer devices and a composition comprising a semiochemical substance. The present invention also relates to the use of this device or kit in a method of diffusing a semiochemical substance to modify behavior in an animal. STATE OF PRIOR ART

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

[0003] These semiochemical substances are chemically sensitive molecules and more particularly sensitive to oxidation (in particular 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 rings. However, the formation of impurities by oxidation processes can have catastrophic effects on the effectiveness of semiochemicals (for example, an attractant can become a repellent or the pheromone of a particular insect can transform 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 greatly depending on the nature of the molecule. For the effect of the mixture to be optimal, each of the molecules that compose it must be diffused in a controlled and balanced manner.

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

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

[0007] Another method of diffusion can be achieved by simply spraying the semiochemical substances onto a support surface. In this case, the user is faced with several distinct technical problems. A first problem is to slow down and control the diffusion over time of the semiochemical substances. A second problem is the formation of an unsightly greasy stain at the spray deposition area. A third problem is the protection of the deposit against inadvertent wiping of the deposit upon contact with an object or fabric.

[0008] To solve this set of technical problems, it is necessary to develop a compact diffuser of semiochemical substances, for example in the form of a thin film, applicable to any type of surface, curved or flat. The latter must make it possible to both constitute a compact reservoir of semiochemical substances with a minimal volume and a large diffusion surface. It must make it possible to control the diffusion of the semiochemical substances over time to extend the duration of effectiveness to 6 to 10 days, and to absorb the semiochemical substances sufficiently quickly (of the order of a few minutes) so as to protect them from accidental wiping by contact with another surface and to be able to be recharged with semiochemical substances. This compact diffuser will advantageously have an aesthetic surface not altered by the deposition of the semiochemical substances.

[0009] The use of polymeric matrices for the release of active substances, in particular semiochemical substances, has been known for a long time since it was already mentioned, for example, in the review by Campion (DG Campion, Pestic. Sci. 1978, 9, 434-440). This publication refers in particular 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.

[0010] Later, other elastomeric matrices were proposed, for example, in 1987, in patent US4,703,070. However, these elastomeric matrices require the incorporation of the active substance 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 for the end of crosslinking or the reactive components of the pre-polymer. However, the activity of semiochemical substances is strongly influenced by even 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 patent US5,504,142. In this case, the matrix is ​​a copolymer of the Pebax® type. Pebax® is a thermoplastic elastomer or a flexible polyamide without plasticizer 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 serving as a vector for the active substance to penetrate into the copolymer matrix. This solvent (derived from undecylenic acid with biocidal properties well known to those skilled in the art) necessary for the implementation of the method 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 prohibitive for the use of such a matrix to store and release semiochemical substances.

[0012] Another 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 capacity to store this molecule, such a copolymer led to very short release times of the active substance, which is incompatible with the long-term releases necessary in 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] Matrices based on ethylene and vinyl acetate copolymers have also been tested to deliver bioactive compounds such as food attractants and pesticides, as described in US Pat. No. 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 achievable with most semiochemical substances which either do not withstand these processing conditions or evaporate quickly at the outlet of the extruder, which makes the load of semiochemical substance 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 not showing sensitivity to peroxides which are necessary for the polymerization of the matrix, that is to say for a limited number of semiochemical substances. Similarly, international application WO2013 / 156249 describes a composition comprising a pesticide and a random copolymer resulting from the copolymerization of acrylic and / or methacrylic acid (monomer A), poly(C2-C6 alkylene glycol) (meth)acrylate (mono-Ci2-C22-alkyl terminated) (monomer B), and Ci-C8-alkyl (meth)acrylate (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 highlighted previously, represents a danger of degradation of semiochemical substances. For example, it is well known that (E,Z)-7,9 dodecadien-nylacetate (sex pheromone of the vine moth) transforms 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 which can be sufficiently softened at a temperature between 45°C and 160°C to incorporate the substances therein. The matrix is ​​formed of 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 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 in 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 which are very sensitive to heat and which will evaporate during this step. In addition, once the insect repellent compound is completely diffused, the composition cannot be recharged.

[0017] EP3187046 describes the use of block copolymers as a support material for diffuse pheromones, block copolymers being used in the form of solid particles or granules of millimeter size. Since the diffusion distance plays a major role in diffusion kinetics, the skilled person would therefore not have used such a material in the form of a thin film because he would have expected that a drastic reduction in the thickness of the material would induce an acceleration drastic reduction in 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 polymer in the form of an acrylic block copolymer and an odorous active compound allowing a release of said odorous active 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 is not described how to integrate such a film into a device for diffusing semiochemical substances.

[0019] There is therefore a need to develop a device for diffusing semiochemical substances which is compact, rechargeable and allows 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-layer 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 polyalkyl methacrylate block and at least one polyalkyl acrylate block, a styrenic block copolymer comprising at least one polystyrene block and at least one optionally hydrogenated polydiene block, or a mixture thereof.

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

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

[0023] This device, thanks to the progressive release of a semiochemical substance, makes it possible to modify the behavior of an animal and in particular to confer a calming effect on pets, such as dogs and cats.

[0024] The active layer of this device is a thin layer (eg a few hundreds of 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, on the surface of this layer). Surprisingly, given its low thickness, the active layer also allows for the effective, controlled and balanced release of this semiochemical substance, even when it is a mixture of active molecules, for example in the context of a pheromone mixture. Indeed, despite the different volatilities of the molecules composing a pheromone mixture, the active layer allows the diffusion speeds of these different molecules to be balanced so as to obtain the desired pheromone activity.

[0025] Once the active substance has been diffused, the device according to the invention, by 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 linked 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 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 makes it possible to conform to any type of surface, whether flat or curved. In addition, its external appearance is preserved over time (no whitening of the active layer, for example), making it possible to maintain the same aesthetics.

[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 also relates to the use of a self-adhesive multilayer device according to the invention or of 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 multilayer device according to the invention to a support, 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 self-adhesive multilayer device, d. optionally, repeat 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 of a kit according to the invention for modifying behavior in an animal. DETAILED DESCRIPTION OF THE INVENTION Self-adhesive multi-layer device

[0031] As indicated above, the self-adhesive multilayer 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 bonded to 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 stuck to any type of support), such materials being well known to those skilled in the art. Thus, the adhesive layers will advantageously comprise, in particular will be constituted by, an acrylic polymer.

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

[0035] The first adhesive layer may further 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 to the chosen support.

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

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

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

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

[0040] This film is further 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 support layer on which it is applied can be seen through transparency. This makes it possible in particular to see any decoration printed on the support layer. Typically, the film material will have a HAZE less than or equal to 20% (measured according to the ISO 13468 standard) and a light transmission (TL) greater than or equal to 80% (measured according to the ISO 13468 standard).

[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 polyalkyl methacrylate block and at least one polyalkyl acrylate block, a styrenic block copolymer comprising at least one polystyrene block and at least one optionally hydrogenated polydiene block, or a mixture thereof. Preferably, the block copolymer is an acrylic block copolymer.

[0043] In the context of the invention, the term "block copolymer", also called "block copolymer", means a copolymer containing, in particular consisting of, a linear sequence of several different blocks, each block consisting of a polymer chain, two adjacent blocks therefore being constituted by different polymer chains. A block copolymer constitutes a single macromolecule, so that each block is covalently linked to the following block, either directly by a covalent bond, or via a constituent unit which 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" is meant a monovalent, linear or branched, saturated hydrocarbon group. The alkyl group advantageously comprises 1 to 10 carbon atoms ((C1-C10)alkyl), in particular 1 to 8 carbon atoms ((C1-C8)alkyl), in particular 1 to 6 carbon atoms ((C1-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 separated by a single single bond), cumulated dienes (double bonds carried by the same carbon atom) or non-conjugated dienes (double bonds separated by two or more single bonds), preferably conjugated. The diene advantageously comprises 4 to 10 carbon atoms, in particular 4 to 8 carbon atoms, especially 4 to 6 carbon atoms, preferably 4 or 5 carbon atoms. It may be, for example, butadiene or isoprene.

[0046] By “polydiene” is meant a polymer resulting from the polymerization of a diene.

[0047] The block copolymer is advantageously a bi-block copolymer or a tri-block copolymer, preferably a tri-block copolymer. When the block copolymer is a tri-block copolymer, it advantageously comprises at most 2 identical blocks, preferably it comprises 2 identical blocks, in particular 2 blocks of polyalkyl methacrylate or polystyrene.

[0048] When the block copolymer is an acrylic block copolymer, the block copolymer comprises at least one polyalkyl methacrylate block and at least one polyalkyl acrylate block.

[0049] The polyalkyl methacrylate is advantageously polymethyl methacrylate (PMMA) and / or the polyalkyl acrylate is advantageously polybutyl acrylate (PABu) or a copolymer of butyl acrylate and 2-ethylhexyl acrylate, preferably is polybutyl acrylate (PABu).

[0050] The acrylic block copolymer is advantageously a bi-block copolymer or a tri-block copolymer, preferably a tri-block copolymer. When the acrylic block copolymer is a tri-block copolymer, it advantageously comprises at most 2 identical blocks, preferably it comprises 2 identical blocks, in particular 2 polyalkyl methacrylate 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 optionally hydrogenated polydiene block.

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

[0054] The styrenic block copolymer is advantageously a bi-block copolymer or a tri-block copolymer, preferably a tri-block copolymer. When the styrenic block copolymer is a tri-block copolymer, it advantageously comprises at most 2 identical blocks, preferably it comprises 2 identical blocks, in particular 2 polystyrene blocks.

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

[0056] The active layer typically has a thickness of 5 μm to 500 μm, in particular of 10 μm to 400 μm, in particular of 20 μm to 300 μm, for example of 50 μm to 250 μm, preferably of 100 μm to 250 μm, for example of approximately 200 μm. 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 comprise 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, in particular when it is 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 stuck to the chosen support. This protective layer, preferably waterproof, may be made of any suitable material well known to those skilled in the art. It may be, for example, 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 expression "semiochemical substance" describes a chemical substance emitted by a plant or an animal into the environment and which has signal value between living beings. It can 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 animal pheromone, in particular a mammalian 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 the location and recognition of a sexual partner, for example.

[0065] Semiochemical substances and more particularly pheromones, are chemical compounds of which a large number of examples (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 animal pheromones. It will more particularly be a volatile substance.

[0067] The expression "volatile" refers to the ability of the semiochemical substance to change from the liquid state to the 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, in particular between 1 Pa and 2500 Pa, more preferably between 1 Pa and 1500 Pa, more preferably between 1 Pa and 1000 Pa, in particular between 1 Pa and 700 Pa.

[0068] For the purposes of the present invention, the term "fatty 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 will advantageously be chosen from 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-dioxaspiro-undecane, benzyl alcohol, Z-(9)-tricosene (muscalure), heneicosane, diacetyl, alkanoic acids having from 5 to 16 carbon atoms (eg caprylic acid, laurylic acid), pinene, methyleugenol, eugenol, 4-methoxy-cinnamaldehyde, estragol, indole, ethyldodecanoate, 4-chloro-2-ethylcyclohexane-carboxylate tert-butyl, 5-chloro-2-ethylcyclohexane-carboxylate tert-butyl, mycrenone, cucurbitacin, trimedlure, (E,E)-8,10-dodecadien-l-ol (codlemone) and mixtures thereof.

[0070] Advantageously, the semiochemical substance may be chosen from ferrugineol, ferrugineone or a ferrugineol-ferrugineone mixture.

[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-tri-decadienyl acetate, [beta]-ionone, 8-methyl-2-decyl propanoate, E,E-9,11-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, E,Z-ll,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, 4-methyl-5-nonanol, 4-methyl-5-nonanone, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol,E-9-dodecadienol, Z-9-dodecadenol, 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-ll-tetradecenol, E-ll-tetradecenol, Z-ll-hexadecenol, Z,E-9,ll-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol, Z,Z-7,ll-hexadecadienol, Z,E-7,ll-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-11-tetradecadienal, E-ll-tetradecadienal, E-ll,13-tetradecadienal, E,E-8,10-tetradecadienal, Z,E-9,ll-tetradecadienal, Z,E-9,12-tetradecadienal, hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, El 1-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, (+)-cis-7,8-epoxy-2-methyloctadecane (disparlure), 3-methyl-2-cyclohexen-1-ol (seudenol), 6-methyl-5-hepten-2-ol (sulcatol), 2-methyl-6-methylene-7-octen-4-ol (ipsenol), 2-methyl-6-methylene-2,7-octadien-4-ol (ipsdienol), cis-2-isopropenyl-1-methylcyclobutane-ethanol (grandiure I), Z- , 3,3-Dimethyl-1-cyclohexane-ethanol (grandiure II), Z-3,3-Dimethyl-1-cyclohexane-acetaldehyde (grandiure III), E-3,3-Dimethyl-1-cyclohexane-acetaldehyde (grandiure IV), cis-4,6,6-trimethylbicyclo[3,1,1]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[3,1,1]hepten-2-ene ([alpha]-pinene), 4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane ([alpha]-caryophyllene), Z-9-tricosene (muscalure), 1'[alpha]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo[3,2,1]octane, 3,3,7-trimethyl-2,9-dioxatricyclo[3,3,1,0]nonane (lineatin), 2-ethyl-1,6-dioxaspiro[4,4]nonane (chalcogran), l,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane (frontalin), rendo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane (endo-brevicomine), rexo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane (exo-brevicomin), (Z)-5-(l-decenyl)dihydro-2-(3H)-furanone, 3,7,1 l-trimethyl-2,6,10-dodecatrien-l-ol (famesol), 3,7,ll-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, 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 may be any 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 animal pheromones, in particular mammalian pheromones.

[0073] The mammals according to the invention are preferably chosen from dogs, cats, horses, cattle and pigs.

[0074] The animal pheromone, in particular mammalian pheromone, can thus be chosen from pheromones of dogs, cats, horses, cattle and pigs.

[0075] Preferably, the animal pheromone is a soothing pheromone.

[0076] Preferably, mammalian pheromones are soothing pheromones such as apaisin which is secreted by females during breastfeeding or facial pheromones in cats.

[0077] Among animal pheromones, one can also distinguish social regulation pheromones such as urinary markers or interdigital feline pheromones to mark their territory. The pheromones according to the invention are natural or synthetic pheromones.

[0078] 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 antioxidant 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.

[0079] The 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.

[0080] The anti-UV agents may be chosen 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-tetramethyl-piperidine, 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, TEMPO from Solvay. These anti-UV agents protect the semiochemicals from degradation by light and can 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.

[0081] The self-adhesive multi-layer device according to the invention may have any size and any shape, depending on the intended application. Kit

[0082] 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.

[0083] According to one embodiment, the self-adhesive multilayer devices according to the invention do not comprise a semiochemical substance.

[0084] The active layer of these devices will advantageously be impregnated with a semiochemical substance using the composition included in the kit. This impregnation may be carried out for example by spraying, by brushing or rolling, or by dipping, preferably by spraying, preferably once the device has been glued to the chosen support.

[0085] The composition, preferably liquid, advantageously comprises, in particular consists of, a semiochemical substance, optionally solubilized in a solvent. The solvent may in particular be an ether such as di(propylene glycol) methyl ether, an alcohol such as isopropanol, etc. Preferably, the composition does not contain of solvent.

[0086] The composition may also comprise one or more antioxidant agents 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.

[0087] Additives such as stabilizers, preservatives or even rheology agents may possibly be present in the composition.

[0088] The composition will preferably be contained in a container allowing it to be sprayed. It may also be contained in a container equipped with a drip system or a brush. Diffusion method

[0089] 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:

[0090] a) the application of a self-adhesive multilayer device according to the invention on a support,

[0091] 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,

[0092] c) diffusion of the semiochemical substance from the active layer of the self-adhesive multilayer device,

[0093] d) optionally, repeating steps b) and c).

[0094] Step a) may be carried out before or after step b). Step a):

[0095] 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 whatever the material of the support.

[0096] Thus, the support may be made of a material chosen from the group consisting of glass, textile, paper, cardboard, plastic, brick, concrete, wood, leather, plant fibers, metal, ceramic, and a combination thereof.

[0097] A support may 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, a glazed expanse such as a window, a piece of furniture, for example a cupboard, or a plastic box.

[0098] A support may also comprise an article, that is to say a discrete or individualized object. This article may be in the form of a stake, a stake, a fence, a palisade, a staple, a hook, a cardboard plate, a glass plate, plastic plate, metal plate, cloth, tarpaulin, bag, transport box, T-shirt, etc. Step b):

[0099] The impregnation of the active layer can be carried out 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.

[0100] Thus, the composition, preferably liquid, will advantageously comprise, in particular will consist of, a semiochemical substance, optionally solubilized in a solvent. Additives such as stabilizers, preservatives or even rheology agents may optionally be present in the composition. The solvent may in particular be an ether such as di(propylene glycol) methyl ether, an alcohol such as isopropanol, etc. Preferably, the composition does not contain a solvent.

[0101] Such contacting can be carried out for example by spraying the composition onto the active layer, by brushing or rolling the active layer with the composition, or by dipping the active layer into the composition.

[0102] Considering the prices of semiochemical substances, an application that limits losses will be favored, such as a spray application. Step c):

[0103] Once the active layer is impregnated with the semiochemical substance, the semiochemical substance will be able to gradually diffuse through this active layer and modify the behavior of an animal in its immediate environment.

[0104] This diffusion will advantageously be spread over a period of 6 to 10 days. Step d):

[0105] An advantage of the device according to the invention is its capacity to be recharged with semiochemical substance, which makes it possible to repeat steps b) and c) one or more times.

[0106] 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

[0107] 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 modifying behavior in an animal.

[0108] Pheromones will influence the behavior of animals such as pets, horses, pigs, which are subject to stressful situations (noise, transport, separation, etc.) related to their environment. The pheromone(s) will be chosen according to the animal (e.g., dog, cat, etc.) for which we wish to modify the behavior according to the situation encountered. For example, the pheromone could be chosen to calm the animal during transport. The animal crate is very often a stressful situation because the animal loses its bearings and is confronted with new stimuli, both olfactory and visual.

[0109] Preferably, the pheromone is an animal pheromone, in particular a mammalian pheromone.

[0110] The mammals according to the invention are preferably chosen from dogs, cats, horses, cattle and pigs.

[0111] The animal pheromone, in particular mammalian pheromone, can thus be chosen from the pheromones of dogs, cats, horses, cattle and pigs.

[0112] Preferably, the animal pheromone is a soothing pheromone.

[0113] Preferably, mammalian pheromones are soothing pheromones such as apaisin which is secreted by females during breastfeeding or facial pheromones in cats.

[0114] Among animal pheromones, we can also distinguish social regulation pheromones such as urinary markers or interdigital feline pheromones to mark their territory.

[0115] The present invention is illustrated by the non-limiting examples below. EXAMPLES

[0116] Example 1: Absorption property as a function of the nature of the impregnation material used

[0117] The materials tested are injected in the form of 5A tensile specimens (ISO 3167). The specimens are weighed and then brought into contact with methyl laurate by dipping them in a methyl laurate bath at a temperature of 20°C. The specimens are recovered after one hour, drained and quickly washed on the surface with ethanol, then dried in the open air and weighed. The difference in weight observed compared to the initial mass of the specimen represents the quantity impregnated. The specimens are then placed in diffusion in a ventilated oven at 30°C for several days. The results are shown in Table 1 below.

[0118] [Tables 1] Material of the specimen M53* PRnew* PMV* PU Quantity impregnated (mg) over 1h 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%)

[0119] * M53 = Nanostrength® M53; PRNEW = Pebax® Rnew; PMV = Pebax® MV (polyether block amide); PU = polyurethane

[0120] 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 has a high adsorption (impregnation) capacity associated with a diffusion of methyl laurate (semiochemical substance) that is sufficiently long and controlled over time (retention capacity).

[0121] Example 2: Physical measurement on 5a specimens made of raw material and material impregnated with methyl laurate

[0122] 5A tensile test specimens are tested on tensile test benches or on a durometer. They have been previously impregnated with methyl laurate (ML) or not according to the method described in Example 1. The impregnation rate is modulated by leaving the specimens in the methyl laurate solution for a longer or shorter time.

[0123] 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 shown in Table 2 below.

[0124] [Tables2] Test specimen Young's modulus (MPa) Elongation at break (%) Shore hardness (deg. Shore from 0 to 100) M53 157 30 37 M53 impregnated with 5% LM 143 43 32 M53 impregnated with 12% LM 48 48 22

[0125] 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

[0126] The objective of this test is to demonstrate the importance of the choice of the thickness of the active layer. For this, two objects made of Nanostrength® M53 of different thicknesses were impregnated with a defined quantity of methyl laurate (ML) at room temperature by depositing the methyl laurate on the surface to be impregnated.

[0127] The first object is a self-adhesive multilayer device according to the invention of 5x5 cm2 comprising:

[0128] - a first adhesive layer of acrylic polymer of approximately 100 m;

[0129] - a layer of paper (cellulose) of approximately 50pm screen-printed with ink;

[0130] - a second adhesive layer of acrylic polymer of approximately 100 m;

[0131] - a Nanostrength® M53 polymer film of approximately 200pm.

[0132] The second object is a 5 x 5 cm2 Nanostrength® M53 plate with a thickness of 5 mm.

[0133] In both cases, the impregnation efficiency is greater than 99%.

[0134] Both objects were diffused at room temperature. The results obtained are shown in Table 3 below.

[0135] [Tables3] Device according to the invention (5x5 cm2) Plate (5x5 cm2) Thickness* 0.2 mm 5 mm Quantity 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

[0136] * Nanostrength® M53 material intended to be impregnated with methyl laurate

[0137] The results show that the device according to the invention diffuses more with a residual amount of methyl laurate of 11% after 144 hours while the thick material shows more than 25% residual methyl laurate. Furthermore, the device according to the invention shows better control of diffusion in the first hours of diffusion.

[0138] Finally, the diffusion efficiency 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 compared to only 73.2% for the thick material.

[0139] 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 in comparison with a thick plate. The diffusion rate is lower at short times and higher at long times, which ensures an instantaneous dose emitted more regularly over time for a thin diffusion system in comparison with a thick diffusion system. Example 4: Liquid semiochemical composition

[0140] Several types of formulation can be envisaged to recharge the self-adhesive multi-layer 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.

[0141] Formulation A facilitates the penetration of the semiochemical substance into the material of the active layer. Formulation B eliminates the need for a solvent since only the semiochemical substance penetrates into the material of the active layer, just like formulation C.

[0142] Example of formulation A:

[0143] 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%).

[0144] 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.

[0145] Example of formulation B:

[0146] In a 50 mL bottle fitted with a spray head are mixed (in %w / w): methyl laurate (2%), methyl oleate (2%) and isopropanol (96%).

[0147] 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%.

[0148] Example of formulation C:

[0149] A mixture of 20 / 80 (w / w) methyl laurate and methyl oleate is introduced into a bottle equipped with a drip device.

[0150] 5 drops of the mixture are placed on the device according to the invention. The rate impregnation measured after 30 min 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 multi-layer device according to claim 2, characterized in that the tri-block copolymer comprises at most 2 identical blocks.

4. A 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 selected 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 animal pheromone, in particular a mammalian 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 μm to 200 μm, in particular of 5 μm to 150 μm, preferably of 10 μm to 100 μm.

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. A method according to claim 13, characterized in that the support is made of a material selected from the group consisting of glass, textile, paper, cardboard, plastic, brick, concrete, wood, leather, plant 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 plastic crate, 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, a transport crate 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 modifying behavior in an animal.