SURFACE-COATED LIQUID COMPOSITION FOR ABSORPTION AND DIFFUSION OF VOLATILE COMPOUNDS

Description

[0001] 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.

[0002] Furthermore, these semiochemical substances are chemically sensitive molecules, particularly susceptible to oxidation (especially in the presence of UV radiation or free radicals) and temperature changes, due to their unsaturated chemical bonds (double or triple bonds), alcohol groups, or stretched ether rings. 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 insect can transform into the pheromone of another).

[0003] One of the major challenges in optimizing the use of these semiochemicals is the ability to store and release them using materials that not only preserve the purity of the semiochemicals during device manufacturing and throughout their lifespan, but also allow for controlled release at sufficient rates over extended periods. Another challenge is the ability to reload the materials multiple times to avoid having to manufacture and use a new item for each new application.

[0004] There are liquid or fluid compositions, such as paints, containing an active compound like an insecticide, designed to be applied to surfaces, such as walls, to allow the compound to diffuse into the surrounding air. However, once the diffusion is complete due to the depletion of the compound in the coating, it is no longer possible to reproduce the diffusion except by applying a new layer of the composition, that is, by applying another coat of paint containing the active compound to be diffused.

[0005] This is cumbersome and expensive because it involves repeated applications of the paint-like composition and layering of coats on the substrate, which is not desirable in the long term.

[0006] The use of polymeric matrices for the release of active substances, particularly semiochemicals, has been known for some time, as it was already discussed, 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.

[0007] Later, other elastomeric matrices were proposed: for example, in 1987, in US patent 4703070. However, these elastomeric matrices require the incorporation of the active substance before the matrix is ​​fully crosslinked. Due to their specific chemical structures (unsaturated bonds, presence of alcohol groups, etc.), few semiochemicals 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 semiochemicals is strongly influenced by even slight deterioration of the molecule (such as a change in isomerism).

[0008] Another thermoplastic matrix for the release of semiochemicals was the subject of a patent application in 1996 (US005504142). In this case, the matrix is ​​a PEBAX®-type copolymer. Pebax® is a thermoplastic elastomer or a flexible, plasticizer-free polyamide composed of a regular linear chain of rigid polyamide segments and flexible polyether segments. However, this type of matrix requires the use of a solvent to act as a carrier for the active substance to penetrate the copolymer matrix. These solvents, necessary for implementing the process described in this invention, are potentially harmful to the environment or may have a negative interaction with animals. The presence of such solvents (derived from undecylenic acid, whose biocidal properties are well known to those skilled in the art) is therefore a prohibitive factor for using such a matrix to store and release semiochemicals.

[0009] Another major 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 demonstrating a high capacity to store this molecule, such a copolymer resulted in 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 (p228 of M. Kah's review in Environment International 63 (2014) 224-235) proposed aqueous formulations based on amphiphilic copolymers containing PEG blocks to release insecticides.However, these aqueous formulations have the disadvantage of not being solid and the presence of water can induce chemical modifications of the semiochemicals.

[0010] Ethylene and vinyl acetate copolymer matrices have also been tested to deliver bioactive compounds such as food attractants and pesticides, as described in US patent 5135744.

[0011] However, the mixing of the copolymer and the bioactive compound and the final shaping (extrusion) must be done at high temperatures (between 80 and 110°C), which is not feasible with most semiochemical substances, which either do not withstand these transformation conditions or evaporate rapidly at the exit of the extruder, making the semiochemical substance load in the plastic difficult to control.

[0012] Other copolymers have also been proposed, for example in WO2012 / 095444, which claims the formation of microcapsules composed of several polymers, including C1-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 the polymerization of the matrix, i.e., for a limited number of semiochemical substances. Similarly, patent WO2013156249A1 describes a composition comprising a pesticide and a statistical copolymer that contains, in polymerized form, acrylic or methacrylic acid (monomer A), a monopoly(C2-6 alkylene alcohol)(meth)acrylate terminated by a C12-C22 alkyl group (monomer B), and a C1-C6 alkyl methacrylate (monomer C). However, this type of statistical copolymer is once again obtained by polymerization with a radical generator (in the examples of this patent of the tert.-butylperpivalate) which, as already highlighted, represents a danger of deterioration of common semiochemical substances. For example, it is well known that (E,Z)-7,9 dodecadienyl acetate (the sex pheromone of the European grapevine moth) is transformed into (E,E)-7,9 dodecadienyl acetate which has no effect on the insect.

[0013] Similarly, document EP0338732 describes a matrix for the release and diffusion of active substances such as perfumes and pheromones into the atmosphere. The matrix is ​​permeable to the active substances and is formed from a copolymer that can be sufficiently softened at a temperature between 45°C and 160°C to incorporate the substances. The matrix consists of a substantially linear sequenced copolymer that is a reaction product of a polydiorganosiloxane, which forms soft segments, and a diisocyanate, which forms hard segments. These soft segments comprise 70 to 99% by weight, based on the weight of the 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.

[0014] Document WO0150859 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 repellent is released from the matrix. The document also describes a fabric substrate containing the composition and a process for preparing the composition. The problem with this type of composition is that solidification involves a drying step at temperatures incompatible with pheromone-type compounds, which are highly sensitive to heat and will evaporate during this step. Furthermore, as noted for other substrates, once the insect repellent compound has been completely diffused, the composition cannot be recharged.

[0015] FR3032972 describes a composition comprising a polymer elastomer phase in the form of an acrylic sequence copolymer and an odorant active compound, methods for absorbing the odorant active compound, and methods for releasing said odorant active compound over a given period of time. This document also describes articles comprising a polymer elastomer phase in the form of an acrylic sequence copolymer and an odorant active compound. However, this document does not describe liquid or fluid compositions, but rather compositions obtained by injection molding, extrusion, co-extrusion, or extrusion / blow molding, resulting in the preparation of profiled parts or elements, blocks, tubes, sheets, or films.

[0016] EP 3 187 046 A1 and FR 3 012 814 A1 disclose a composition comprising a polymer elastomer phase and an active fragrance compound, wherein said active fragrance compound is released over a given period of time. The elastomer phase is formed from blocks of a sequenced acrylic copolymer.

[0017] The present invention therefore proposes a new type of liquid composition, similar to paint or ink, which can be applied to any substrate and forms a solid—or at least cohesive—surface coating. This coating can be loaded with a semiochemical compound and then gradually release said compound over extended periods. Furthermore, once the diffusion of said compound is complete, the coating can be recharged with the semiochemical substance simply by bringing said substance into contact with the coating. This allows for the adsorption, protection, and controlled release of said semiochemical substance repeatedly over long periods.

[0018] Thus, the present invention aims, firstly, at a method for diffusing a semiochemical substance comprising the following steps: a. provision of a solid composition comprising a polymeric resin, an optional filler and an optional pigment, b. Contacting a composition comprising a semiochemical substance with the solid composition, c. Impregnation of the solid composition by the composition comprising the semiochemical substance, d. Diffusion of said semiochemical substance from the solid composition, e. optionally, repetition of steps b to d.

[0019] The method according to the invention is characterized in that the solid composition comprising a polymeric resin further comprises at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block; said copolymer being dispersed and immobilized in the polymeric resin.

[0020] Typically the alkyl is a C1-C10 alkyl, especially C1-C8, linear or branched.

[0021] The method according to the invention is characterized in that step a) is preceded by steps α1) to α3); step α1) comprising the supply of a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, and optionally at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block; step α2) comprising the application of the liquid composition to a support; and step α3) comprising the evaporation of the solvent. Typically, the alkyl is a C1-C10 alkyl, in particular C1-C8, linear or branched.

[0022] A "filler" is an ingredient that is inert to semiochemical compounds. It is generally a white or slightly colored mineral substance of natural origin, in the form of very fine particles that are practically insoluble in the composition's medium. The filler serves, for example, to thicken the composition, improve its adhesion, provide an aesthetic appearance, or limit shrinkage once the solvent has evaporated and the composition has solidified. The filler can be chosen from the group consisting of talc, carbonates, clays, and mixtures thereof.

[0023] Polymer resins are commonly used in compositions such as screen printing inks and include cellulose resins, vinyl resins, and polyurethane resins, whether one- or two-component. Cellulose resins typically include nitrocellulose resins of ethylcellulose, cellulose acetobutyrate, or cellulose acetopropionate, and may be combined with other resins such as alkyds, polyesters, polyurethanes, or polyamides. Vinyl resins typically include polyvinyl acetates, polyvinyl chlorides, vinyl acetate / vinyl chloride copolymers, and polyvinyl ethers.

[0024] A thin film, within the scope of the present invention, is understood to be a layer whose thickness is between 5 and 500 µm, in particular between 10 and 400 µm, or even between 20 and 300 µm, or even between 50 and 250 µm. This thickness may vary depending on the viscosity and composition of the composition, the nature of the substrate, and the number of applications on said substrate.

[0025] The term "solid composition" here refers, as opposed to a "liquid composition," to a composition that does not flow under its own weight and is not deformable by its own weight; a solid composition can thus be semi-rigid or flexible. Conversely, a "liquid" (or fluid) composition is a composition that can flow under its own weight, be poured, or transferred. In the context of this invention, a liquid (or fluid) composition corresponds to a composition such as paint or ink, for example.

[0026] The method according to the invention is also characterized in that the solid composition is bonded to a support, in particular in the form of a thin layer which adheres to said support on which it has been applied and hardened.

[0027] According to a particular embodiment, the support is made of a material chosen from the group including glass, textile, paper, cardboard, plastic, brick, metal and ceramic.

[0028] The term support here refers to any material element that is covered in whole or in part by the solid composition.

[0029] A support can include or consist of a continuous surface, more or less extensive and more or less flat, such as a wall, opaque or transparent, for example a wall, a floor or a glazed surface such as a window.

[0030] A support can also include an article, that is to say a discrete or individualized object, the surface of which will be coated, in whole or in part, by the solid composition.

[0031] Thus, an article comprising a solid composition is also described. The article may be made of glass, textiles, paper, cardboard, plastic, brick, metal, or ceramic.

[0032] An item can take the form of a mat, a cushion, a basket, a blanket, a collar, a harness, a saddle, a toy, a ball, a balloon, a plush toy, a rope, a ring, a trunk, a tower, for example.

[0033] According to an advantageous embodiment, the method according to the invention is characterized in that the acrylic block copolymer is a bi-block copolymer or a tri-block copolymer.

[0034] More specifically, the tri-block copolymer comprises at most 2 identical blocks.

[0035] Advantageously, alkyl polymethacrylate is methyl polymethacrylate (PMMA).

[0036] Advantageously still, the alkyl polyacrylate is chosen from the group consisting of butyl polyacrylate (PABu) and a copolymer of butyl acrylate and 2-ethylhexyl acrylate.

[0037] More specifically, the acrylic block copolymer is a tri-block copolymer of the PMMA-PABu-PMMA type.

[0038] In the context of the present invention, the term "block polymer" refers to a polymer whose macromolecules are composed of linearly linked blocks. The blocks can be assembled directly or via a constituent unit that is not an integral part of the blocks.

[0039] In the context of the present invention, the expression "block copolymer" represents a block copolymer derived from several species of polymers.

[0040] In the context of the present invention, the term "block" represents the part of a macromolecule comprising a plurality of constituent units and which has at least one particularity of constitution or configuration which does not appear in the adjacent parts.

[0041] The expression "semiochemical substance" refers to a chemical substance emitted by a plant or animal into the environment and which has signal value between living beings.

[0042] The expression "composition comprising a semiochemical substance" refers to a composition, typically a liquid composition, which comprises, or consists of, one or more semiochemical substances, possibly solubilized in a solvent.

[0043] Semiochemicals are classified into pheromones—which enable communication between individuals of the same species—and allomones, kairomones, and synomones, which are exchanged between animals or plants belonging to different species. Semiochemicals can be perceived by smell (for volatile compounds) or by taste (for non-volatile compounds). The information carried by semiochemicals can, for example, allow for the location and recognition of a sexual partner.

[0044] Semiochemical substances, and more specifically pheromones, are chemical compounds of which a large number of examples (8000) are given in the online database Pherobase (www.pherobase.com).

[0045] According to one embodiment of the invention, the semiochemical substance is a volatile semiochemical substance, in particular a fatty chain volatile semiochemical substance, and is advantageously chosen from the group of pheromones.

[0046] In a particularly preferred manner, the volatile semiochemical substance is lipophilic and is a fatty chain pheromone.

[0047] The term "fatty chain" is understood in the context of the present invention to mean a linear or branched aliphatic hydrocarbon chain, possibly unsaturated, comprising 5 to 18, 6 to 16 or 5 to 16 carbon atoms, thus giving a lipophilic character to the semiochemical substance.

[0048] The term "volatile" refers to the high volatility of a semiochemical substance that can easily transition from a liquid to a gaseous state under ambient pressure and temperature conditions, i.e., approximately 20°C and 760 mm Hg. A "volatile" liquid is defined as one whose saturated vapor pressure at 20°C is greater than 0.01 mm Hg, preferably between 0.01 and 20, more preferably between 0.01 and 10, and most preferably between 0.01 and 5.

[0049] Examples of fatty-chain pheromones include pheromones known and usable according to the present invention: volatile alkanols and alkenols having 5 to 18 carbons, volatile alkanals and alkenals having 5 to 18 carbons, alkanones having 6 to 18 carbons, 1,7-dioxaspirononane, 3- or 4-hydroxy-1,7-dioxaspiro-undecane, benzyl alcohol, Z-(9)-tricosene (muscature), heneicosene, diacetyl or alkanoic acids having 5 to 16 carbons such as caprylic acid, lauryl acid, pinene, methyleugenol, ethyl dodecanoate, tert-butyl 4-(or 5-)chloro-2-ethylcyclohexane carboxylate, mycrenone, cucurbitacin, trimedlure and (E,E)-8,10-dodecadian-1-ol (codemone).

[0050] Advantageously, the volatile semiochemical substance can be chosen from ferrugineol, ferrugineone, or a ferrugineol-ferrugineone mixture.

[0051] Other examples of known fatty-chain pheromones include: 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, 4-methoxycinnamaldehyde, [beta]-ionone, estragole, eugenol, indole, 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-7,11-hexadecadienyl acetate, Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate, Z,Z-11,13-hexadecadienyl acetate, Y,Z-11,13-hexadecadienyl acetate, Z,E-3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate, E,E-3,13-octadecadienyl acetate, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E-6-nonenol, 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-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadienol, E,Z-8,10-dodecadienol, Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, the Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol, Z,Z-7,11-hexadecadienol, Z,E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal, tetradecanal, Z-7-tetradecenal, Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E,E-8,10-tetradecadienal, Z, E-9,11-tetradecadienal, the Z, E-9,12-tetradecadienal, the hexadecanal, the Z-8-hexadecenal, the Z-9-hexadecenal, the Z-10-hexadecenal,E-10-hexadecenal, Z-11-hexadecenal, E-11-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, the Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3-methyl butanoate, disparlure: (+) cis-7,8-epoxy-2-methyloctadecane, seudenol: 3-methyl-2-cyclohexen-1-ol, sulcatol: 6-methyl-5-hepten-2-ol, ipsenol: 2-methyl-6-methylene-7-octen-4-ol, ipsdienol: 2-methyl-6-methylene-2,7-octadien-4-ol, Grandure I: cis-2-isopropenyl-1-methylcyclobutane-ethanol, Grandure II: Z-3,3-dimethyl-1-cyclohexane-ethanol, Grandure III: Z-3,3-dimethyl-1-cyclohexane-acetaldehyde, size IV: E-3,3-dimethyl-1-cyclohexane-acetaldehyde,cis-2-ver-benol: cis-4,6,6-trimethylbicyclo[3,1,1]hept-3-en-2-ol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, cucurbitacin, 2-methyl-3-buten-2-ol, 4-methyl-3-heptanol, [alpha]-pinene: 2,6,6-trimethylbicyclo[3,1,1]hepten-2-ene, [alpha]-caryophyllene: 4,11,11-trimethyl-8-methylene-bicyclo[7,2,0]undecane, Z-9-tricosene, [alpha]-multistriatin, 2-(2-endo,4-endo)-5-ethyl-2,4-dimethyl-6,8-dioxabicyclo [3,2,1]octane, methyleugenol: 1,2-dimethoxy-4-(2-propenyl)phenol, lineatin: 3,3,7-trimethyl-2,9-dioxatriculo[3,3,1,0]nonane, chalcogran: 2-ethyl-1,6-dioxaspiro[4,4]nonane, frontalin: 1,5-dimethyl-6,8-dioxabicyclo[3,2,1]octane, endo-brevicomine: endo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, exo-brevicomine: exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3,2,1]octane, (Z)-5-(1-decenyl)dihydro-2-(3H)-furanone, the farnesol: 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, nerolidol 3,7-11-trimethyl-1,6,10-dodecatrien-3-ol,3-Methyl,6-(1-methylethenyl)-9-decen-1-ol acetate, (Z)-3-methyl-6-(1-methylethenyl)-3, 9-decadien-1-ol acetate, (E)-3,9-methyl-6-(1-methylethenyl)-5,8-decadien-1-ol acetate, 3-methylene-7-methylocten-1-ol propionate, (Z)-3,7-dimethyl-2,7-octadien-1-ol propionate, (Z)-3,9-dimethyl-6-(1-methylethenyl)-3,9-decadien-1-ol.,

[0052] In another embodiment of the present invention, the volatile semiochemical substance is an animal pheromone, in particular a mammalian pheromone.

[0053] The mammals according to the invention are preferentially chosen from dogs, cats, horses, cattle and pigs.

[0054] Animal pheromones, particularly those from mammals, can thus be chosen from among the pheromones of dogs, cats, horses, cattle and pigs.

[0055] Preferably, animal pheromones are calming pheromones.

[0056] Preferably, mammalian pheromones are calming pheromones such as apaisin, which is secreted by females during breastfeeding, or facial pheromones in cats.

[0057] Among animal pheromones, one can also distinguish social regulation pheromones such as urinary markers or feline interdigital pheromones used to mark territory. The pheromones according to the invention are natural or synthetic.

[0058] In a particular embodiment of the invention, the semiochemical substance can be protected against the action of light and / or oxygen. Indeed, when the diffusing articles according to the invention are used in cultures for several months, it may be preferable to protect the semiochemical substance from deterioration over time. Those skilled in the art are accustomed to adding antioxidants and UV stabilizers to semiochemical substances to fulfill this function. An advantage of the process according to the invention is that the UV stabilizers or antioxidants can already be contained in the liquid composition before its application to a support or its impregnation by the semiochemical compound, or added to the composition comprising the semiochemical substance before the latter is incorporated / adsorbed into / by the polymeric composition.These two methods ensure intimate protection of the semiochemical substance until its diffusion into the external environment.

[0059] Antioxidants can be chosen from the group consisting of vitamin E, butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT), used alone or in combination. These antioxidants protect the semiochemical substance from degradation and can be added in quantities, expressed as a percentage by weight of the liquid or solid composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5% and 2%.

[0060] UV-blocking additives can be selected from the group consisting of beta-carotene, p-aminobenzoic acid, hindered amines, and hindered alkoxyamines, used alone or in mixtures. These UV blockers protect semiochemicals from degradation by light and can be added in quantities, as a percentage by weight of the composition, ranging from approximately 0.1% to approximately 3%, particularly between 0.5% and 2%.

[0061] As mentioned, the method according to the invention is characterized in that the pheromone is an animal pheromone, in particular a calming pheromone of mammals.

[0062] Thus, according to an advantageous embodiment of the invention, the method is characterized in that step d) of diffusing said semiochemical substance from the impregnated solid composition is carried out in the animal's living space and that the method calms the animal. As such, the solid composition can be applied to a support chosen from the group including, for example, a mat, a cushion, a basket, a blanket, a transport crate, a kennel, or a barrier.

[0063] Furthermore, according to one embodiment of the invention, the support onto which the liquid composition according to the invention is applied comprises an article that is in contact with the animal or used by the animal. Thus, a support for the composition according to the invention can be chosen from the group including, for example, a collar, a harness, a jacket, a coat, a saddle, or a blanket.

[0064] The support for the solid composition may also include an item with which the animal interacts, and the support is then chosen from the group including toy, ball, balloon, plush toy, rope, ring, cat tree, trunk, tower, for example.

[0065] The present invention also relates to a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, at least one semiochemical substance and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, characterized in that the polymeric resin is selected from the group comprising cellulosic resins, vinyl resins and polyurethane resins, one- or two-component.

[0066] Such a liquid composition is thus presented in the form of a paint or ink type composition for surface coating which allows the coating of a support.

[0067] By coating we mean here that the liquid composition is applied to a solid support which will be coated in part or totally by the liquid composition which will solidify following the evaporation of the solvent and will form the solid composition.

[0068] Another advantage of the composition according to the invention is that it can be applied to any type of object.

[0069] Indeed, its liquid (or fluid) nature allows it to be applied to any surface and to cover all or part of a given support. Thus, it is possible to apply it to a solid or flexible support such as a collar, fabric, stake, bar, plate, or plaque made of any material, for example, depending on the intended use and location.

[0070] The application can be carried out by roller, brush, spraying, dipping or any other suitable means allowing the support to be coated in whole or in part with the fluid composition.

[0071] The ease of application of the liquid composition according to the invention also allows it to be used as a paint or ink and to carry out any application on any support, in particular textile, to cover it in whole or in part, or even to define logos or inscriptions, according to the will or desire of the user.

[0072] Thus the liquid composition according to the invention can be used in a printing method by the screen printing techniques known to a person skilled in the art, and this to screen print any support of their choice and whatever the material, for example on clothes, toys or any utensil for example.

[0073] The liquid composition then solidifies via solvent evaporation, resulting in a solid composition in the form of a surface coating comprising, or consisting of, a continuous phase of polymeric resin in which is dispersed the optional pigment, the optional filler, at least one optional acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, as well as the optional semiochemical substance.

[0074] The liquid composition according to the invention is also characterized in that the semiochemical substance represents between 0% and 80% by weight of the liquid composition, particularly between 1% and 60%, and even more particularly between 5% and 50%.

[0075] The substrates coated with the solid composition, if it does not already contain the semiochemical compound, can then be impregnated and charged with a composition comprising a semiochemical substance.

[0076] This impregnation, or loading, can be achieved by simply bringing the solid composition into contact with a composition containing a semiochemical compound. In particular, the composition containing said semiochemical compound is in the form of a liquid composition containing said semiochemical compound and is brought into contact with the solid composition.

[0077] Such contact can be achieved by spraying a liquid composition including the semiochemical compound, but also by brushing or rolling or by soaking, for example.

[0078] It goes without saying that, given the prices of semiochemical substances, an application that limits losses will be favoured, and thus an application by sprinkling or spraying will be more advantageous.

[0079] Another particularly important advantage of the composition is that the solid composition can be charged and / or recharged by a semiochemical substance, such as a pheromone.

[0080] Indeed, once the initial quantity of semiochemical compound, absorbed by the solid composition—or initially present in the liquid composition—has been released and diffused, it is possible to recover the solid composition or the substrate coated with the solid composition (regardless of its form) and re-impregnate said composition with the semiochemical compound according to the process described above. Similarly, a wall coated with the solid composition can be re-impregnated with a composition containing a semiochemical substance by contact, as explained earlier.

[0081] Thus, a manufacturing process for a solid composition containing a semiochemical substance is also described, comprising the following steps: provide a solid composition comprising a polymeric resin constituting a continuous phase in which is dispersed and immobilized at least one acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, an optional filler and an optional pigment; bring said composition into contact with a composition comprising a semiochemical substance for a time and at a temperature permitting the impregnation of said solid composition by said substance, recover said solid composition impregnated with semiochemical substance.

[0082] The solid composition is also characterized in that once impregnated by the semiochemical substance, the latter represents between 1% and 80% by weight of the solid composition, particularly between 1 and 50%, between 5 and 50%, more particularly between 5 and 40%, or even between 5 and 30%, or between 5 and 20%.

[0083] A solid composition can thus diffuse and gradually release the semiochemical substance into the environment until the quantity of the contained substance is exhausted. It can then be reused for recharging as described above, followed by further diffusion. And this can be repeated several times.

[0084] This advantage is very important because it allows for the recycling of substrates coated with the solid composition, which makes both economic and ecological sense.

[0085] The inventors observed that a solid polymer resin composition such as the one described above had the capacity to absorb and release a semiochemical substance. The addition of acrylic block copolymers significantly enhances this property but is not essential to achieve the technical effect of impregnation / absorption and release.

[0086] The acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block is found dispersed within the continuous resin phase in the form of inclusions which will contribute to capturing, absorbing, retaining and releasing the semiochemical substance.

[0087] Thus, a solid composition is also described, characterized in that the polymeric resin constitutes a continuous phase in which is dispersed and immobilized at least one acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, the optional filler and the optional pigment.

[0088] Finally, the invention relates to the use of a liquid composition for the diffusion of said semiochemical substance, wherein the liquid composition comprises at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, at least one semiochemical substance and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, characterized in that the polymeric resin is selected from the group comprising cellulosic resins, vinyl resins and polyurethane resins, single or two-component.

[0089] The invention finally aims at the use of a liquid composition according to the invention for the absorption and diffusion of a semiochemical substance, wherein the liquid composition comprises at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, at least one semiochemical substance and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, characterized in that the polymeric resin is selected from the group comprising cellulosic resins, vinyl resins and polyurethane resins, single or two-component. EXAMPLES

[0090] Materials and raw materials: The block copolymer materials are materials from the nanostrenth® range sold by Arkema, such as M53, M65, or M53F. The pheromones are synthesized by M2i Development or M2i Salin using methods already reported in the literature. The pheromone of Lobesia botrana (grape berry moth) is 7E,9Z-dodecadienyl acetate (CAS: 54364-62-4) with a molar mass of 224.34 g / mol. Methyl laurate (CAS 111-82-0) with a molar mass of 214.34 g / mol is one of the components of the calming pheromonal composition of FELIWAY. The commercial inks are purchased from TIFLEX.

[0091] Example 1: Demonstration of the retention effect on block copolymer films: A 20% wt. solution of M53 block copolymer in ethyl acetate is prepared. Using a glass pipette, 10 mL of the solution is deposited into a 10 cm diameter aluminum tray. The tray is placed in a ventilated oven for 24 h. A homogeneous film of block copolymer is obtained. Ten trays are prepared in this way and numbered from 1 to 20.

[0092] On trays numbered 1 to 5, 100 mg of lobesia pheromone (7E,9Z-dodecadienyl acetate) is deposited. On trays numbered 6 to 10, 100 mg of methyl laurate is deposited. Both active ingredients are applied to the film using a spray of a 20% pentane-diluted pheromone solution. The trays are left exposed to air until the active ingredient is no longer visible. The trays are then placed in a ventilated oven maintained at 40°C (lobesia) or 30°C (methyl laurate). Two blank trays are loaded with the same quantity of each active ingredient.

[0093] The trays are regularly analyzed to determine the residual pheromone level (by simple weighing or preferably by gas chromatography).

[0094] Table 1 below shows the diffusion time in the oven required to reach below 10% of residual active ingredient relative to the quantity introduced. [Table 1] Bare tray (reference) 1 2 3 4 5 6 7 8 9 10 Lobesia (%res) 72h - - - - - 720h 696h 744h 720h 672h Methyl laurate (%res) 24h 240h 264h 226h 240h 240h - - - - -

[0095] This example shows the retention effect of a surface treated by a block copolymer film deposition compared to an untreated surface.

[0096] Example 2: Demonstration of the effect of copobloc by comparing a non-additized ink of block copolymers with an added ink.

[0097] Square glass plates, 10 cm on each side, were screen-printed using two commercial inks: blue polyworks (TIFLEX) and vinyl (TIFLEX). One set of plates was used untreated, while the other was treated by spraying with a 10% solution of M53 block copolymers without ethyl acetate. Once dried, these plates showed no visual difference from the untreated plates. All four sets of plates were sprayed with lobesia pheromone and methyl laurate in a 20% pentane solution. The plates were left to air dry and then placed in a ventilated oven at 30°C and 40°C, respectively, for the lobesia pheromone-impregnated plates and the methyl laurate-impregnated plates. The trays are regularly analyzed to determine the residual pheromone level (by simple weighing or preferably by gas chromatography).

[0098] Table 2 below shows the diffusion time in the oven required to reach below 10% of residual active ingredient relative to the quantity introduced. [Table 2] Polyworks Ink Vinyl ink Bare tray (reference e) Copoblo additive-free With copoblo additive c Copoblo additive-free With copoblo additive c Copoblo additive-free With copoblo additive c Copoblo additive-free With copoblo c 8 additive Lobesi has (%res) 72 h 72h 168h - - 72h 168h - - Methy l laurat e (%res) 24 h - - 24h 96h - - 24h 96h

[0099] This example shows the retention effect of an ink-coated surface with added block copolymer compared to an untreated surface and an ink-coated surface.

Claims

1. Method for diffusing a semiochemical substance comprising the following steps: a. providing a solid composition comprising a polymeric resin, an optional filler and an optional pigment, b. bringing a composition comprising a semiochemical substance into contact with the solid composition, c. impregnating the solid composition with the composition comprising the semiochemical substance, d. diffusing said semiochemical substance from the solid composition, e. optionally repeating steps b to d, characterized in that the solid composition comprising a polymeric resin further comprises at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block; said copolymer being dispersed and immobilized in the polymeric resin, characterized in that step a) is preceded by steps α1) to α3); step α1) comprising providing a liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block; step α2) comprising applying the liquid composition on a substrate and step α3) comprising evaporating the solvent.

2. Method according to claim 1, characterized in that the solid composition is secured to a substrate, in particular in the form of a thin layer with a thickness of between 5 and 500 µm.

3. Method according to claim 2, characterized in that the substrate is made of a material selected from the group comprising glass, textile, paper, cardboard, plastics, metal and ceramic.

4. Method according to one of claims 1 to 3, characterized in that the acrylic block copolymer is a bi-block copolymer or a tri-block copolymer.

5. Method according to one of claims 1 to 4, characterized in that the tri-block copolymer comprises at most 2 identical blocks.

6. Method according to one of claims 1 to 5, characterized in that the alkyl polymethacrylate is polymethyl methacrylate (PMMA).

7. Method according to one of claims 1 to 6, characterized in that the alkyl polyacrylate is selected from the group consisting of poly butyl acrylate (PABu) and a copolymer of butyl acrylate and 2-ethylhexyl acrylate.

8. Method according to one of claims 1 to 7, characterized in that the acrylic block copolymer is a tri-block copolymer of the PMMA-PABu-PMMA type.

9. Method according to one of claims 1 to 8, characterized in that the semiochemical substance is an animal pheromone.

10. Method according to claim 9, characterized in that the animal pheromone is selected from pheromones of dogs, cats, horses, cattle and pigs.

11. Method according to one of claims 9 and 10, characterized in that the animal pheromone is an appeasing pheromone.

12. Method according to one of claims 9 to 11, characterized in that step d.) of diffusing said semiochemical substance from the impregnated solid composition is carried out at the living environment of an animal.

13. Method according to claim 12, characterized in that the solid composition according to the invention is applied on a substrate selected from the group comprising a mat, a cushion, a basket, a cover, a transport case, a pet house, a barrier, a collar, a harness, a jacket, a mantle, a saddle.

14. Liquid composition comprising at least one polymeric resin, at least one solvent, optionally at least one pigment, optionally at least one filler, optionally at least one semiochemical substance and at least one acrylic block copolymer, said acrylic block copolymer comprising at least one alkyl polymethacrylate block and at least one alkyl polyacrylate block, characterized in that the polymeric resin is selected from the group comprising cellulosic resins, vinyl resins and polyurethane, mono or bicomponent resins.

15. Use of a composition according to claim 14 for diffusing said semiochemical substance.

16. Use of a composition according to claim 14 for absorbing and diffusing a semiochemical substance.