EP2406329A1 - Aqueous formulation for an antifouling coating system for submerged substrates, method for treating same, and use thereof - Google Patents

Aqueous formulation for an antifouling coating system for submerged substrates, method for treating same, and use thereof

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Publication number
EP2406329A1
EP2406329A1 EP10713479A EP10713479A EP2406329A1 EP 2406329 A1 EP2406329 A1 EP 2406329A1 EP 10713479 A EP10713479 A EP 10713479A EP 10713479 A EP10713479 A EP 10713479A EP 2406329 A1 EP2406329 A1 EP 2406329A1
Authority
EP
European Patent Office
Prior art keywords
weight
formulation
formulation according
resin
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10713479A
Other languages
German (de)
French (fr)
Inventor
Véronique ROULLEAUX
Patrick Frangoulis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seawax Marine Coatings
Original Assignee
Seawax Marine Coatings
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Seawax Marine Coatings filed Critical Seawax Marine Coatings
Publication of EP2406329A1 publication Critical patent/EP2406329A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the invention relates to a formulation of an antifouling coating system for application to immersed substrates, a method of treatment with such a carrier formulation to be immersed, and the use of such a formulation as an antifoulant.
  • a formulation of an antifouling coating system for application to immersed substrates, a method of treatment with such a carrier formulation to be immersed, and the use of such a formulation as an antifoulant.
  • the sea in the broad sense namely a vast expanse of salt water, and even soft waters are naturally rich in proteins and polysaccharides mainly produced by the plankton and excreta of the multitude of aquatic organisms that the it can be found in sea water.
  • the surface of the sea, or fresh water, when it is not very agitated, is thus covered with a permanent bio film.
  • the suspended elements are deposited on any immersed support in the form of a film of the thickness of one to a few microns, after only a few seconds or minutes in a rich medium.
  • This film provides microscopic bacteria, micro-algae and aquatic fungi, so-called pioneer organisms, a first source of food.
  • the last layer of paint or coating applied for example to the hull of a boat before launching is preferably of the anti-fouling type. Indeed, this protects the submerged part of the hull against the fixation of these marine organisms.
  • any user may inhale these particles, for example when using a spray gun, or when sanding the antifouling layer of a hull, or by passing through the skin following projections or contact with the paint, or more rarely via accidental ingestion, or even more rarely by voluntarily mouthing scales of paint (for example, phenomenon known as "Pica").
  • Such antifouling paints can also induce indirect toxicity in humans, by ingestion of filtering shells such as mussels, oysters, cockles, etc.
  • biocide-based anti-fouling paints must always be done with protection of the skin and mucous membranes (waterproof clothing, glasses, gloves) and respiratory protection (cartridge mask).
  • Such biocide-based anti-fouling paints thus contain one or more toxic molecules and prove to be polluting.
  • TBT Tributyltin
  • organochlorines such as dichlorophenyl dimethyl urea (diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine have been found in particular.
  • Biocide-free anti-fouling coatings having anti-adhesion properties against fixation of marine organisms based for example on liquid organosilicones, or liquid paraffin, or fluorinated oils in combination with organopolysilicon polymers have been tested and developed. .
  • the mode of action of these coatings is based on the low surface tension of the silicone and on the more or less controlled release of the lubricating additives used to prevent the fixation of marine organisms.
  • the effectiveness of these antifouling coatings is limited.
  • Another disadvantage is their low mechanical loading capacity, which is frequently accompanied by insufficient adhesion to anticorrosive coatings, requiring the application of an intermediate layer of hooked.
  • US 6,413,446 relates more particularly to an antifouling agent comprising in particular carbosiloxanes, alkoxysilanes, an organic solvent and / or water, a catalyst, inorganic nanoparticles as well as lubricating additives.
  • this agent appears to include only a very small amount of non-stick lubricating agent in addition to the silicone resins.
  • Patent EP 0563939 discloses a silicone resin formulation, a silicone fluid and a solvent for forming an antifouling coating in which the silicone fluid forms a liquid interface above the resin layer and prevents fauna and flora to attach firmly to the surface of the support.
  • Such an antifouling coating has a phase shift and is not homogeneous.
  • EP 1829943 discloses an anti-fouling coating composed of a composition comprising an organopolysiloxane and paraffin or a silicone oil. The paraffin or silicone oil exudes on the surface of the film formed by the coating and contributes to the anti-fouling performance.
  • Such an antifouling coating also has a phase shift and is not homogeneous.
  • JP 08081524 discloses an anti-fouling composition
  • a silicone resin emulsion and optionally an oil-based wax or emulsion.
  • such compositions do not prove stable over time.
  • a problem to be solved by the invention is to implement a new formulation of an anti-fouling coating system intended to be easily applied to submerged supports, able to limit the fixation of marine organisms as efficiently as possible. that the paints containing biocides, sealed, stable over time and homogeneous to a single phase, and which does not have the undesirable effects observed in the prior art.
  • an aqueous, hydrophobic and oleophobic, single-phase homogeneous formulation intended to be applied to supports present in an aqueous medium presents a remarkable anti-fouling activity to disadvantage the fixation of marine organisms, is waterproof and stable over time, providing a new alternative, while respecting the environment and human health.
  • the formulation according to the invention offers the following advantages in particular with respect to the prior art:
  • the formulation contains no toxic biocide and does not have the undesirable effects of the paints containing them; - the formulation is respectful of the environment; the formulation has a flash point greater than 55 ° C., and is considered as non-flammable;
  • the formulation offers advantages in terms of transport safety, storage and use; the formulation is in hydrophobic, oleophobic and homogeneous aqueous phase with a single phase;
  • the formulation makes it possible to effectively protect the immersed part of any support against the fixation of marine organisms and their possible degradation; - the formulation limits the introduction of pathogens via marine organisms with the development of maritime transport; the formulation is particularly suitable for application on ship hulls so as to reduce weight and water resistance, reduce hydrodynamic drag, increase speed, decrease fuel consumption, and decrease frequency of cleaning ;
  • the formulation is applied to a hull optionally coated with an anticorrosive
  • the invention therefore firstly relates to a formulation of an anti-fouling coating system intended to be applied to immersed supports, characterized in that it comprises at least 30% by weight of the total weight of water, at least 10% by weight of dry extract of the total weight of a water repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight an anti-adherent active agent.
  • its second object is a process for treating substrates intended to be immersed with a formulation according to the invention, characterized in that the formulation is applied in at least one layer by spraying, with a roller or with a brush, on the support to be protected against marine fouling, after cleaning and prior drying of the support, at an outside temperature of between approximately 5 ° and approximately 50 ° C., preferably between approximately 15 ° and approximately 30 ° C. then is dried at room temperature, for example 23 0 C, for about 25 minutes and about 40 minutes between two successive layers, and between about 30 minutes and about 50 minutes before launching.
  • composition according to the invention of an anti-fouling coating system is intended to be applied to submerged supports.
  • Non-limiting examples of submerged supports include all objects or constructions intended to be immersed in a marine environment such as hulls of boats or ships, engine bases, propellers, propeller shafts, floats, the piers of wharves or pontoons, buoys, or any measuring or shooting equipment suitable for being immersed.
  • formulation according to the invention applies to any type of surface, for example wood, any metal, such as for example aluminum and iron, any metal alloy such as steel, polyester, glass, earthenware, or even concrete.
  • the formulation according to the invention comprises at least 30% by weight of the total weight of water, at least 10% by weight of dry extract of the total weight of a water-repellent chosen from a silicone resin, a polyurethane resin and / or a acrylic styrene copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight of an antiadhesive active agent.
  • a water-repellent chosen from a silicone resin, a polyurethane resin and / or a acrylic styrene copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight of an antiadhesive active agent.
  • the formulation according to the invention comprises at least 30% water.
  • the formulation comprises at least 50% of a solvent-co-solvent system comprising predominantly water.
  • the solvent-co-solvent system according to the invention comprises at least one non-aqueous compound chosen from hydrocarbons, alcohols, ketones and esters, taken alone or in combination.
  • the solvent-co-solvent system comprises at least 20% of a non-aqueous compound chosen from hydrocarbons, alcohols, ketones and esters, taken alone or in combination.
  • hydrocarbon solvents having 2 to 24 carbon atoms, paraffinic, isoparaffinic, cycloparaffinic hydrocarbons such as hydrotreated heavy naphtha, and aromatics such as xylene. , preferably a C8 to C10 naphtha co-solvent and a deflavored aliphatic hydrocarbon.
  • alcohols according to the invention mention may be made of an alcoholic hydrocarbon having 2 to 20 carbon atoms, preferably ethanol, isopropanol or butanol or else monopropylene glycol.
  • the aqueous solvent-co-solvent system according to the invention is thus hydroalcoholic.
  • the solvent-co-solvent system according to the invention advantageously has antifreeze properties, conferred in particular by monopropylene glycol.
  • N-methyl pyrrolidone may be mentioned preferentially.
  • ester As non-limiting examples of the ester according to the invention, mention may preferably be made of rapeseed methyl ester, even more preferably a mixture of oleate and methyl linoleate.
  • aqueous solvent-co-solvent system used according to the invention is therefore chosen so as to be suitable and necessary to obtain a homogeneous mixture with a single phase with one of the water-repellent chosen from a silicone resin, a polyurethane resin and / or a resin. acrylic styrene copolymer, taken alone or in admixture and the antiadhesive active agent.
  • the non-aqueous co-solvent is chosen from solvents of class 3 which are non-flammable at ambient temperature, with a flash point greater than 55 ° C.
  • non-aqueous co-solvent of class 3 mention may be made of N-methyl pyrrolidone.
  • Such a non-aqueous co-solvent used according to the invention is therefore chosen so as to be suitable and necessary to obtain a homogeneous mixture at a single phase with the water-repellent chosen from a silicone resin, a polyurethane resin and / or a copolymer resin. acrylic styrene, and the anti-adherent active agent by solubilizing them, to promote the anti-adhesion effect on the immersed support and to obtain a formulation having a flash point greater than 55 ° C.
  • the formulation comprises a solvent-co-solvent system essentially comprising water, ie at least 80% by weight of the weight of the solvent-water co-solvent system. According to an exemplary embodiment of the invention, the formulation comprises at least 50% by weight of the total weight of water.
  • the formulation according to the invention also comprises at least 10% by weight of dry extract of the total weight of a water-repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture.
  • a water-repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture.
  • the amount of water-repellent chosen from a silicone resin, polyurethane resin and / or acrylic styrene copolymer, taken alone or as a mixture, and in particular for the silicone or polyurethane resin, is advantageously considered in the aqueous or solvent phase.
  • the formulation according to the invention may thus comprise less than 10% of silicone resin-based water repellant or of polyurethane resin or acrylic styrene copolymer resin considered independently of one another by weight of dry extract of the total weight, the mixture of two types of resins or of the three types of resins being at least 10% by weight of dry extract of the total weight of the formulation.
  • the waterproofing agent based on silicone resin according to the invention is a siloxane resin, polysiloxane and / or their derivatives, taken alone or as a mixture, in the aqueous phase or in the solvent phase, preferably in the aqueous, nonionic phase.
  • silicone resin according to the invention mention may preferably be made of polymethylsiloxane or polydimethylsiloxane resin, in aqueous or solvent phase.
  • the waterproofing agent based on silicone resin, polyurethane and / or styrene acrylic copolymer according to the invention, hydrophobic, is chosen so as to allow the cohesion of the anti-fouling coating film on its support.
  • the water-repellent according to the invention is a mixture of about 2% of a solution of polymethylsiloxane resin with 70% of active material in the solvent phase or 44 to 50% phase aqueous, preferably in aqueous phase, and about 12% of a polymethylsiloxane resin in aqueous or solvent emulsion, preferably in aqueous emulsion.
  • the waterproofing agent based on silicone resin is a polymethylsiloxane resin in aqueous nonionic emulsion.
  • the polymethylsiloxane resin is 40% by weight of solids and thus comprises about 60% water.
  • the water-repellent is a polyurethane resin, preferably in aqueous emulsion, even more preferably at 50% by weight of dry extract and thus about 50% of water or at 35% by weight of dry extract, taken alone or in combination with a styrene-acrylic copolymer resin and / or a silicone resin, preferably in aqueous emulsion, for example at 40% by weight of solids.
  • the water-repellent is even more preferably a styrene acrylic copolymer resin taken alone.
  • Such hydrophobic water-repellent based on polyurethane resin and / or acrylic styrene copolymer used according to the invention is thus chosen so as to promote adhesion between the support, optionally coated with a primary layer of hooked or a anticorrosive layer, and the anti-fouling coating layer and also between the different layers of antifouling coating, and also increase the water resistance.
  • the formulation according to the invention also comprises at least 5% by weight of dry extract of the total weight of an anti-adherent active agent.
  • the amount of antiadhesive active agent is advantageously considered in aqueous or solvent phase, preferably aqueous.
  • the formulation according to the invention thus comprises at least about 5% by weight of dry extract of anti-adherent active agent of the total weight.
  • the formulation may comprise about 10%, about 15% or about 20% dry extract of antiadhesive active agent of the total weight.
  • the antiadhering active agent according to the invention is chosen from fatty compounds such as waxes, fats or paraffins, natural or synthetic, having a dropping point of between 30 ° and 100 ° C.
  • the antiadhering active agent according to the invention may be in solid form, for example powder or pellets, viscous or liquid, preferably in the form of dispersion or aqueous emulsion.
  • Such an aqueous dispersion or emulsion of antiadhesive active agent makes it possible to solubilize the antiadhesive active agent and to avoid phase shift phenomena in the formulation according to the invention.
  • waxes By way of non-limiting examples of waxes, mention may be made of carnauba wax, of plant origin, having a melting point of between 78 ° and 85 ° C., one of the highest of the waxes of natural origin. and a very high hardness, and beeswax having a melting point of 64 ° C.
  • lanolin of animal origin obtained by purification and refining of the suint.
  • the antiadhering active agent according to the invention is a paraffin, even more preferably a paraffin 56/58, that is to say having a drop point at about 56 -58 0 C.
  • the formulation comprises about 20% by weight of dry extract of antiadhesive active agent and about 40% when it is in aqueous emulsion at 50%.
  • paraffin as an anti-adhesion agent is known for its problems of low cohesion between the layers deposited successively and requires the implementation of specific adjuvants to overcome this problem. It is also difficult to adhere such a fatty substance as paraffin on a support.
  • the combination of solvent-co-solvent used in the formulation according to the invention makes it possible to obtain a homogeneous formulation with a single phase.
  • the formulation according to the invention is thus homogeneous, in a single phase, before and after application, and stable over time. Indeed, this aqueous solvent-co-solvent system dilutes and solubilizes the hydrophobic compounds so that, after stirring, one or more homogeneous layers can be applied to the surface of the support to be treated, capable of being immersed.
  • the anti-fouling coating thus obtained after application forms a solid, homogeneous layer with a single phase.
  • the use of a low content of non-aqueous co-solvent, less than 5% by weight of the total weight, such as N-methyl pyrrolidone, taken alone or in combination with ethanol allows to obtain a perfectly homogeneous mixture at a single phase with the water repellent and the active anti-adherent agent, stable, without phase shift phenomenon over time.
  • N-methyl pyrrolidone which is a coalescing agent also helps to form the antifouling coating film and ethanol to accelerate the drying times.
  • the formulation according to the invention has a flash point greater than 55 ° C., in particular by choosing a suitable solvent-co-solvent system essentially comprising water and a co-solvent comprising ester.
  • rapeseed methyl a mixture of oleate and methyl linoleate, or a mixture of C8 to ClO naphtha and a deflated aliphatic hydrocarbon, or a solvent-co-solvent system comprising essentially water, for example at least 80% by weight of the solvent-co-solvent system, and optionally a small amount of N-methyl pyrrolidone, less than 5%, taken alone or in combination.
  • the formulation is thus considered as nonflammable.
  • the formulation according to the invention non-flammable and non-toxic, offers advantages in terms of safety of transport, storage and use, not requiring special precautions adapted.
  • the formulation according to the invention also comprises a non-toxic repellent agent, natural, able to repel the grip especially of algae, and other marine organisms and crustaceans, on the immersed surface to be protected.
  • repellent agents include essential oils, for example menthol, camphor, tea tree, geranium, thyme, bay leaf, peppermint oil, or the like. Grapefruit seed extracts.
  • the non-toxic agent, natural, able to repel the grip especially of algae is composed of bacterial strains at a concentration of less than 5% by weight of the total weight, preferably between 0.1 and 0.5%.
  • ecological algicidal products may be mentioned. Such products are perfectly miscible in aqueous solution, retain their properties insofar as they are not degraded by unsuitable organic solvents and make it possible to maintain a formulation according to the homogeneous invention before and after application.
  • the formulation according to the invention is also capable of comprising the following constituents: silica oxide and / or talc which gives hardness and distributes the antiadhesive active agent in the dry film in addition to stabilizing it in the liquid anti-fouling coating; a surfactant, able to prevent phase shift and to allow miscibility between water and the various solvents and co-solvents, and in particular allowing the dispersion of silica, and / or talc and paraffin wax, preferably a water-soluble, non-ionic, water-soluble hydrophilic and hypophile wetting coupling agent, preferably ethoxylated octylphenol comprising about 11 moles of ethylene oxide or a sodium acrylate polymer-based agent or an anionic surfactant; a thickener, preferably a liquid polyurethane in aqueous solution, or an acrylic thickener which are rheological agents for adjusting the rheology for optimum application by brush, brush or roller; an anti-corro
  • dye By way of nonlimiting examples of dye, mention may be made of iron chromium hematite (brown), cobalt chromite green spinel (green), cobalt aluminate spinel (blue), copper chromium black spinel (black), dioxide Titanium (white), insoluble in aqueous phase.
  • inorganic, inorganic pigments, insoluble in the aqueous phase advantageously confers an opacity to the formulation to be applied so as to modify the external appearance of the surface of the support to be treated.
  • the formulation according to the invention may also optionally include traces of a biocide such as chloromethyl isothiazoline, which is an anti-mold preservative for the protection of the formulation during its storage, for example in a pot .
  • traces is meant a concentration less than or equal to 0.01%.
  • the formulation contains no trace of biocide.
  • the wetting agent is added to the water with slow stirring
  • the silica oxide powder and / or talc powder are optionally impregnated with a repellent agent such as an essential oil or a compound of bacterial strains;
  • the rheology is adjusted with one or more thickeners so as to obtain the desired appearance for the formulation having a density, for example of 1.01, and a viscosity, for example Brookfield of 1.8 dPa.s at 23 ° C. C or flat cone 0.4 dPa.s at 25 °
  • the active anti-adherent agent for example paraffin
  • the solvents and co-solvents used according to the invention the methyl ester of rapeseed, a mixture of oleate and methyl linoleate, except for water; .
  • This dissolution is carried out with powerful stirring;
  • water repellent for example the resin solution polymethylsiloxane containing 70% of active material in the solvent phase, the thickener, the second part of the water-repellent, for example the polymethylsiloxane resin in aqueous emulsion, the antifreeze and then the biocide; then, the surfactant is added, for example octylphenol ethoxylated;
  • a dye for example an inorganic pigment.
  • the formulation according to the invention is advantageously in liquid form, 'the form of an emulsion or gel form.
  • the formulation according to the invention is packaged in any container capable of receiving a liquid or a gel, such as for example a pot.
  • the formulation can be advantageously stirred before each application so as to obtain a perfectly homogeneous mixture in a single phase.
  • the formulation is preferably applied to smooth surfaces, even painted for example with a hard-matrix or erodible matrix antifouling paint or semi-erodible matrix or previously coated with an anticorrosive, previously cleaned and dried.
  • the formulation is applied in at least one layer by spraying with an electric spray gun or with a manual sprayer, roller or brush, or with a cloth, on the support to be protected against marine fouling.
  • the formulation is applied by carrying out cross-movements, horizontal and vertical, so as to treat and moisten the support without reloading the already treated areas.
  • the formulation is applied in a very thin layer.
  • one liter is sufficient to treat about 8 to 10 m 2 , or 12 m 2 with a layer, for example a layer of 7.7 m 2 , a layer of about 120 microns wet thickness, when applied with a brush and 11.3 m 2 , or a layer of about 90 microns wet thickness, during an application to the lacquer roller.
  • the formulation is preferably applied in a dry place, at an outside temperature of between approximately 5 ° and approximately 50 ° C., preferably between approximately 15 ° and approximately 30 ° C. After application, it is allowed to dry at room temperature, for example 23 ° C. 0 C, for about 25 minutes and about 40 minutes between two successive layers, and between about 30 minutes and about 50 minutes before launching after applying the last layer.
  • the tools used to apply the formulation according to the invention are then easily cleaned with water and such cleaning does not induce any risk of pollution.
  • the formulation according to the invention is without risk of toxicity to the user and easy to use, the user does not require any particular protection.
  • the formulation according to the invention by the water content of at least 30% by weight of the total weight of the formulation provides an antifouling coating that does not peel off during its application. Indeed, in the case of use on imperfectly dry substrates of organic solvents in antifouling coating compositions, moisture trapped between the support and the coating layer inevitably leads to poor adhesion, detachment of the coating and attack and degradation of the support, solvents evaporating faster than water during drying. In contrast, the aqueous formulation according to the invention can be applied to an imperfectly dry support by evaporation of the water trapped under the coating during drying simultaneously with the evaporation of the water included in the formulation.
  • a coating is obtained waterproof anti-fouling which does not reabsorb water during the immersion of the treated support. Also, during drying, the antiadhesive active agent becomes solid and forms with the rest of the formulation an adherent, homogeneous, solid and dry layer. The release agent is thus not exuded on the surface of the antifouling coating layer obtained according to the invention.
  • a test carried out with application of a layer of the formulation according to the invention of 100 ⁇ m wet thickness on glass and after measurement with the BK drying recorder at a suitable speed evidenced evaporation of solvents after 6 min, a surface drying time of the coating according to the invention after 10 min, a start of core drying after 39 min and a total drying after 47 min, under standard drying conditions at room temperature.
  • three layers are preferably applied during the first use.
  • the life of the treatment is 12 months in the marine environment, prolonged parking outside the water does not affect the effectiveness of the treatment.
  • the formulation does not contain pigment or dye, and does not change the color of the support after application.
  • the formulation according to the invention is resistant to abrasion.
  • a first test carried out with application of a layer of the formulation according to Example 1 of the invention of 150 microns wet thickness on a primer of 150 microns thick, and after accelerated drying 48h at standard conditions followed by 48h in a chamber at 40 0 C, after 200 cycles of friction, has demonstrated a mean loss of antifouling coating film thickness according to the invention of 16 microns.
  • the treatment is renewed each year, by application of two new layers of the formulation according to the invention.
  • the formulation according to the invention forms, after application, an anti-fouling coating layer intended to disadvantage the adhesion of marine organisms such as algae, shells and other crustaceans on the treated submerged supports.
  • the formulation makes the gripping surface very smooth and facilitates their quick release either by a simple cleaning, without having to scratch or to make the slightest effort, and even simply when moving the ship for example.
  • a vessel sailing regularly will keep its own hull by the simple friction of the water on the hull.
  • a ship not sailing regularly thanks to the technical properties of the formulation, self cleans while sailing and therefore does not require specific cleaning binding.
  • a smooth shell thus treated with the formulation according to the invention offers less resistance to progress, such a treatment to reduce the hydrodynamic drag, increase speed and reduce fuel consumption.
  • 1 to 2 mm of algae and organisms attached to a hull cause a loss of speed of about 15%.
  • the fixed organisms deteriorating the surface of the hulls, whether made of wood, metal or resin the formulation aims to protect them while decreasing their frequency of cleaning.
  • Example 1 (liquid aspect) acrylic styrene copolymer resin
  • Example 4 gel appearance: 40% polymethylsiloxane resin in aqueous nonionic emulsion
  • Example 6 (liquid aspect): 40% polymethylsiloxane resin in aqueous nonionic emulsion
  • the examples of above formulations may advantageously comprise about 0.2% of a dye such as an inorganic pigment, for example iron chromium hematite (brown), cobalt chromite green spinel (green), cobalt aluminate spinel (blue), the copper chrome black spinel
  • a dye such as an inorganic pigment, for example iron chromium hematite (brown), cobalt chromite green spinel (green), cobalt aluminate spinel (blue), the copper chrome black spinel
  • the invention is illustrated by the efficiency test below, carried out in the Port Camille Rayon of Golfe-Juan (Rocher-Maritimes), port in shallow water, very closed, without circulation of water, and very loaded in vase.
  • This test aims to highlight the effectiveness of the formulation according to the invention as anti-fouling agent intended to disadvantage the adhesion of marine organisms such as algae, shells and other crustaceans on any submerged support.
  • the test is carried out with small plates (30 cm * 20 cm), made of marine plywood, initially coated on both sides with a white epoxy primer layer, immersed to a depth of approximately 1.50 m.
  • the wafer A is coated with the formulation according to the invention as defined above in Example 9, aqueous, hydrophobic and super oleophobic, transparent; and the plate B is coated with an antifouling paint based on copper salts, substances now banned by the European REACH standard, from INTERNATIONAL group AKZO NOBEL, reference CRUISER UNO blue.
  • Figures IA and IB highlight the appearance of the wafer A and the plate B before their launch. Both pads A and B appear completely clean, free of any dirt and other marine deposits.
  • FIGS. 2A and 2B respectively show the appearance of these same plates A and B after 64 days of immersion in seawater. According to the results obtained, the plate A, on which three layers of the formulation were applied according to the invention is covered with a slight vase deposit and does not involve any colonization by barnacles or barnacles.
  • the plate B is covered with a vase deposit similar to that obtained on the plate A, and does not involve any colonization by barnacles or barnacles.
  • the wafer A treated with the formulation according to the invention, according to the results obtained from the test carried out, thus disadvantages the grip of marine organisms such as algae, shells and other crustaceans, and limits the deposit for example of silt.
  • the formulation according to the invention thus offers a new alternative anti-fouling coating having an efficiency comparable to a biocide-based antifouling paint while improving respect for the environment and human health.
  • the invention is not limited to the embodiments and to the examples presented above, and the person skilled in the art, by virtue of routine operations, may be led to make other embodiments that are not explicitly described. which fall within the broad scope of the invention.

Abstract

The invention relates to a formulation for an antifouling coating system to be applied on submerged substrates. The invention is characterised in that the formulation contains at least 30 wt % of water relative to the total weight thereof, at least 10 wt % relative to the total weight thereof of a dry extract of a waterproofing agent selected from a silicone resin, a polyurethane resin, and/or a styrene acrylic copolymer resin either alone or mixed, and at least 5 wt % relative to the total weight thereof of a dry extract of an active anti-adhesion agent. The invention also relates to a method for processing substrates to be submerged using such a formulation, and to the use of such a formulation as an antifouling agent for deterring the attachment of marine organisms such as algae, shellfish and other crustaceans on any submerged substrate, and in particular ship hulls.

Description

FORMULATION AQUEUSE D'UN SYSTEME DE REVETEMENT ANTISALISSURE DE SUPPORTS IMMERGES, SON PROCEDE DE TRAITEMENT ET SON AQUEOUS FORMULATION OF AN ANTI-SLIP COATING SYSTEM FOR SUBMERSIBLE SUBSTRATES, PROCESSING METHOD AND SAME
UTILISATIONUSE
L'invention concerne une formulation d'un système de revêtement antisalissure destinée à être appliquée à des supports immergés, un procédé de traitement avec une telle formulation de supports destinés à être immergés, ainsi que l'utilisation d'une telle formulation comme agent antisalissure destiné à défavoriser l'accroche des organismes marins tels que les algues, coquillages et autres crustacés sur tout support immergé et notamment les carènes des navires.The invention relates to a formulation of an antifouling coating system for application to immersed substrates, a method of treatment with such a carrier formulation to be immersed, and the use of such a formulation as an antifoulant. intended to disadvantage the attachment of marine organisms such as algae, shells and other crustaceans on any submerged support and in particular the hulls of the ships.
Il existe une colonisation spontanée d'un support immergé par les organismes marins. C'est un phénomène absolument normal sous l'eau, notamment dans les couches éclairées et riches en nutriment.There is a spontaneous colonization of a support submerged by marine organisms. This is an absolutely normal phenomenon under water, especially in the light and nutrient-rich layers.
En effet, la mer au sens large, à savoir une vaste étendue d'eau salée, et moindrement les eaux douces sont naturellement riches en protéines et en polysaccharides principalement produits par le plancton et les excréta de la multitude d'organismes aquatiques que l'on peut trouver dans l'eau de mer. La surface de la mer, ou des eaux douces, quand elle n'est pas très agitée, est ainsi couverte d'un bio film permanent. Sous l'eau, les éléments en suspension se déposent sur tout support immergé sous forme d'un film de l'épaisseur d'un à quelques microns, après seulement quelques secondes ou quelques minutes dans un milieu riche. Ce film fournit à certaines bactéries, micro-algues et champignons aquatiques microscopiques, dits organismes pionniers, une première source de nourriture. Ces derniers vont enrichir cette pellicule qui va s'épaissir 'en un bio film mucilagineux plus épais, devenant un substrat de plus en plus complexe pour des colonies de protozoaires puis d'organismes fixés ou mobiles (macro-algues, larves d'invertébrés et de vertébrés), dont des espèces incrustantes qui deviendront elles-mêmes support pour d'autres espèces. De plus, de nombreuses larves d'organismes marins ont d'étonnantes capacités de fixation, même sur des supports vivants, souples et très mobiles, telles que les balanes sur la peau des baleines .Indeed, the sea in the broad sense, namely a vast expanse of salt water, and even soft waters are naturally rich in proteins and polysaccharides mainly produced by the plankton and excreta of the multitude of aquatic organisms that the it can be found in sea water. The surface of the sea, or fresh water, when it is not very agitated, is thus covered with a permanent bio film. Underwater, the suspended elements are deposited on any immersed support in the form of a film of the thickness of one to a few microns, after only a few seconds or minutes in a rich medium. This film provides microscopic bacteria, micro-algae and aquatic fungi, so-called pioneer organisms, a first source of food. The latter will enrich this film, which will thicken into a thicker mucilaginous bio film, becoming an increasingly complex substrate for colonies of protozoa then fixed or mobile organisms (macroalgae, invertebrate larvae and of vertebrates), including encrusting species that will become support for other species. In addition, many larvae of marine organisms have amazing attachment abilities, even on media alive, supple and very mobile, such as barnacles on the skin of whales.
Ainsi, il est connu que la dernière couche de peinture ou de revêtement appliquée par exemple à la carène d'un bateau avant sa mise à l'eau est préférentiellement du type antisalissure. En effet, ceci permet de protéger la partie immergée de la coque contre la fixation de ces organismes marins .Thus, it is known that the last layer of paint or coating applied for example to the hull of a boat before launching is preferably of the anti-fouling type. Indeed, this protects the submerged part of the hull against the fixation of these marine organisms.
Toutefois, la plupart des peintures et autres revêtements antisalissure disponibles sur le marché, et notamment avant l'établissement des nouvelles normes environnementales en vigueur à ce jour, sont confectionnés principalement avec des biocides, produits de base extrêmement nocifs pour l'environnement et l'Homme. Ils sont néfastes d'une part, pour l'environnement marin ou fluvial empoisonnant ainsi la faune et la flore et, d'autre part, pour la personne qui les applique ou qui les nettoie.However, most paints and other anti-fouling coatings available on the market, and especially before the establishment of the new environmental standards in force today, are made mainly with biocides, which are extremely harmful to the environment and the environment. Man. They are harmful on the one hand, for the marine or fluvial environment thus poisoning the fauna and flora and, on the other hand, for the person who applies or cleans them.
Ainsi, ces peintures pourraient contribuer à certains phénomènes de dystrophisation et de pullulation d'espèces indésirables. Les espèces de phytoplancton et zooplancton les plus sensibles aux biocides disparaissent au profit d'algues indésirables ou toxiques. Certains biocides et d'autres polluants peuvent également s'accumuler dans le bio film qui se forme à la surface des eaux calmes et être « exportés » avec les embruns vers le littoral et les terres intérieures lors des tempêtes, au point d'affecter voire de tuer les plantes les plus fragiles de la bande côtière.Thus, these paintings could contribute to certain phenomena of dystrophication and proliferation of undesirable species. The most biocidal species of phytoplankton and zooplankton disappear in favor of unwanted or toxic algae. Some biocides and other pollutants can also accumulate in the bio-film that forms on the surface of calm waters and be "exported" with spray to the coast and inland during storms, to the point of affecting or even to kill the most fragile plants in the coastal strip.
Par ailleurs, les risques immédiats pour la personne qui les manipule sont irritatifs pulmonaires, allergiques et cutanés. On parle dans ce cas de toxicité directe pour l'Homme. En effet, sans protection adéquate, tout utilisateur risque ainsi d'inhaler ces particules, par exemple lors de l'utilisation d'un pistolet à peinture, ou lors du ponçage de la couche antisalissure d'une carène, ou par passage au travers de la peau suite à des projections ou contact avec la peinture, ou plus rarement via une ingestion accidentelle, ou encore plus rarement en portant volontairement à la bouche des écailles de peinture (par exemple, phénomène dit du « Pica ») . De telles peintures antisalissure peuvent induire également une toxicité indirecte chez l'Homme, par ingestion de coquillages filtreurs tels que des moules, huîtres, coques, etc. ou d'autres fruits de mer ou poissons ayant grandi en aval de sites de carénage (peinture ou décapage de coques de navires) ou à proximité d'épaves immergées. La consommation régulière de fruits de mer contaminés est susceptible d'induire des maladies aigϋes ou chroniques liés aux métaux lourds. Concernant les risques à long terme, ils sont encore mal connus, mais pourraient inclure des maladies dégénérâtives, auto-immunes, ou encore des cancers.In addition, the immediate risks for the person handling them are pulmonary, allergic and cutaneous irritants. In this case, we speak of direct toxicity to humans. Indeed, without adequate protection, any user may inhale these particles, for example when using a spray gun, or when sanding the antifouling layer of a hull, or by passing through the skin following projections or contact with the paint, or more rarely via accidental ingestion, or even more rarely by voluntarily mouthing scales of paint (for example, phenomenon known as "Pica"). Such antifouling paints can also induce indirect toxicity in humans, by ingestion of filtering shells such as mussels, oysters, cockles, etc. or other seafood or fish that has grown downstream from the refit sites (painting or stripping hulls of ships) or near submerged shipwrecks. Regular consumption of contaminated seafood is likely to induce acute or chronic diseases related to heavy metals. Regarding long-term risks, they are still poorly known, but could include degenerative diseases, autoimmune, or cancer.
L'application de peintures antisalissure à base de biocide doit donc toujours se faire avec une protection de la peau et des muqueuses (vêtements étanches, lunettes, gants) et une protection respiratoire (masque à cartouche) .The application of biocide-based anti-fouling paints must always be done with protection of the skin and mucous membranes (waterproof clothing, glasses, gloves) and respiratory protection (cartridge mask).
De plus, la décomposition de la plupart des peintures antisalissure à base de biocide par le feu, ayant avec un point éclair inférieur à 550C et donc considérées comme inflammables, conduit également à l'émission de gaz, fumées et cendres hautement toxiques .In addition, the decomposition of most fire-resistant antifouling paints, with a flash point below 55 0 C and therefore considered flammable, also leads to the emission of gases, fumes and highly toxic ash.
De telles peintures antisalissure à base de biocide contiennent ainsi une ou plusieurs molécules toxiques et s'avèrent être polluantes.Such biocide-based anti-fouling paints thus contain one or more toxic molecules and prove to be polluting.
On connaît en particulier le tributylétain (TBT) , très efficace, qui a été le biocide le plus utilisé en marine dans le monde. Toutefois, ce produit, ses molécules de dégradation et ses métabolites se sont révélés gravement et durablement polluants au point de décimer des populations naturelles de coquillages et de perturber la reproduction de nombreuses espèces . Le TBT induit notamment chez certains organismes un phénomène d' imposexe à des dilutions très faibles, inférieures au ng/L. Les résidus du TBT, dont l'étain, non biodégradable, persistent longtemps dans les sédiments des ports et sur les sites d'immersion de boues de dragage, et à leur aval suite aux remises en suspension le cas échéant. Pour ces raisons, en novembre 1999, une résolution de l'0MI (A.895) a été proposée, adoptée le 5 octobre 2001, interdisant les peintures antisalissure à base d'étain à compter du 1er janvier 2003. Leur présence sur la coque d'un navire est ainsi interdite depuis 2008.Tributyltin (TBT), which is very effective and has been the most widely used biocide in the world, is particularly known. However, this product, its degradation molecules and its metabolites have been found to be severely and sustainably polluting to the point of decimating natural shellfish populations and disrupting the reproduction of many species. In particular, TBT induces in certain organisms a phenomenon of impositionxe at very low dilutions, lower than ng / L. TBT residues, including tin, which are non-biodegradable, persist for a long time in harbor sediments and dredge sludge disposal sites, and are subsequently accepted. resuspension if necessary. For these reasons, in November 1999, a resolution of IMO (A.895) was proposed, adopted on October 5, 2001, banning tin-based anti-fouling paints as of January 1, 2003. Their presence on the hull ship has been banned since 2008.
On connaît également d'autres peintures antisalissure, de la famille des biocides, qui s'avèrent moins toxiques, mais qui néanmoins le restent. En effet, selon l'European Commission Project « Assessment of Antifouling Agents in Coastal Environment », les analyses des résidus relargués dans l'eau par ces peintures mettent en évidence la présence notamment de cuivre sous forme d'oxyde cuivreux, de dioxyde de cuivre, de thiocyanate de cuivre, d'acrylate de cuivre, de poudre de cuivre en flocon, d'hydroxyde de cuivre, de zinc sous forme de zinc pyrithione, de cupronickel, ou encore de colophane (rosine ou rosin) . Aussi, parmi les biocides relargués dans l'eau, on a surtout trouvé des organochlorés tels que du dichlorophenyl dimethyl urée (diuron) , du 2- methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazineOther anti-fouling paints, from the family of biocides, are also known, which prove to be less toxic, but which nevertheless remain so. Indeed, according to the European Commission Project "Assessment of Antifouling Agents in Coastal Environment", analyzes of residues released in water by these paints highlight the presence in particular of copper in the form of cuprous oxide, copper dioxide , copper thiocyanate, copper acrylate, flake copper powder, copper hydroxide, zinc in the form of zinc pyrithione, cupronickel, or rosin (rosin or rosin). Also, among the biocides released into the water, organochlorines such as dichlorophenyl dimethyl urea (diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine have been found in particular.
(Irgarol 1051®), du 2 , 4 , 5, 6-tetrachloroisophtalonitrile(Irgarol 1051 ®) of 2, 4, 5, 6-tetrachloroisophthalonitrile
(chlorothalonil) , du 4,5 dichloro-2-n-octyl-4-isothiazolin-3- one (Seanine 211® ; Kathon 5287®) , du dichlorofluoro methylthiodimethyl phenyl sulfamide (dichlofluanid) . On a aussi trouvé du 2-thiocyanomethylthio benzothiazole (TCMTB) , du 2, 3, 5, 6-tetrachloro-4-sulfuronyl pyridine (TCMS pyridine) , du dithio carbamate de zinc (zineb) , du trioxyde d'arsenic, moins souvent et en moindre quantité . Ces biocides sont parfois associés entre eux et/ou avec du cuivre pour obtenir des effets synergiques, et renforcer ou élargir leur spectre d'action.(chlorothalonil), 4,5 dichloro-2-n-octyl-4-isothiazolin-3-one (Seanine 211 ®; Kathon ® 5287) of dichlorofluoro methylthiodimethyl phenyl sulfamide (dichlofluanid). 2-Thiocyanomethylthio benzothiazole (TCMTB), 2,3,5,6-tetrachloro-4-sulfuronyl pyridine (TCMS pyridine), zinc dithio carbamate (zineb), arsenic trioxide, were also found less frequently. and in smaller quantities. These biocides are sometimes associated with each other and / or with copper to obtain synergistic effects, and to reinforce or broaden their spectrum of action.
D'une manière générale, il existe une réelle demande quant à fournir des produits ou préparations dépourvus de biocide toxique, beaucoup moins nocifs pour la santé humaine et animale, et tout aussi efficaces. Dans le contexte actuel, notamment dans le cadre de la réglementation des biocides, il est d' intérêt de trouver une peinture ou revêtement antisalissure, moins irritant et moins toxique, au moins aussi efficace que les peintures contenant des biocides, et ne présentant pas les effets indésirables des peintures selon l'art antérieur.In general, there is a real demand to provide products or preparations free of toxic biocide, much less harmful to human and animal health, and just as effective. In the current context, particularly in the context of the regulation of biocides, it is It is of interest to find an antifouling paint or coating, less irritating and less toxic, at least as effective as paints containing biocides, and not exhibiting the undesirable effects of paints according to the prior art.
On a testé et développé des revêtements antisalissure dépourvus de biocide ayant des propriétés anti-adhésion contre la fixation des organismes marins, basé par exemple sur des organosilicones liquides, ou de la paraffine liquide, ou des huiles fluorées en combinaison avec des polymères de type organopolysilicône . Le mode d'action de ces revêtements est basé sur la basse tension superficielle de la silicone et sur le relargage plus ou moins contrôlé des additifs de lubrification utilisés pour prévenir la fixation des organismes marins. Cependant, l'efficacité de ces revêtements antisalissure est limitée. Un autre inconvénient est leur basse capacité de chargement mécanique, qui est fréquemment accompagnée d'une adhérence insuffisante aux revêtements anticorrosifs, nécessitant l'application d'une couche intermédiaire d'accroché.Biocide-free anti-fouling coatings having anti-adhesion properties against fixation of marine organisms, based for example on liquid organosilicones, or liquid paraffin, or fluorinated oils in combination with organopolysilicon polymers have been tested and developed. . The mode of action of these coatings is based on the low surface tension of the silicone and on the more or less controlled release of the lubricating additives used to prevent the fixation of marine organisms. However, the effectiveness of these antifouling coatings is limited. Another disadvantage is their low mechanical loading capacity, which is frequently accompanied by insufficient adhesion to anticorrosive coatings, requiring the application of an intermediate layer of hooked.
On connaît plus particulièrement le document US 6,413,446 qui concerne un agent antisalissure comprenant notamment des carbosiloxanes, des alkoxysilanes, un solvant organique et/ou de l'eau, un catalyseur, des nanoparticules inorganiques ainsi que des additifs lubrifiants. Toutefois, cet agent n'apparaît comprendre qu'une très faible quantité d'agent lubrifiant anti-adhérent en plus des résines silicones.US 6,413,446 relates more particularly to an antifouling agent comprising in particular carbosiloxanes, alkoxysilanes, an organic solvent and / or water, a catalyst, inorganic nanoparticles as well as lubricating additives. However, this agent appears to include only a very small amount of non-stick lubricating agent in addition to the silicone resins.
On connaît le document EP 0563939 qui divulgue une formulation à base de résine silicone, d'un fluide silicone et d'un solvant pour former un revêtement antisalissure dans lequel le fluide silicone forme une interface liquide au- dessus de la couche de résine et empêche à la faune et la flore de s'attacher fermement à la surface du support. Un tel revêtement antisalissure présente un déphasage et n'est pas homogène . On connaît également le document EP 1829943 qui divulgue un revêtement antisalissure composé d'une composition comprenant un organopolysiloxane et de la paraffine ou une huile silicone. La paraffine ou l'huile silicone exsudent à la surface du film formé par le revêtement et contribuent à la performance antisalissure. Un tel revêtement antisalissure présente également un déphasage et n'est pas homogène.Document EP 0563939 discloses a silicone resin formulation, a silicone fluid and a solvent for forming an antifouling coating in which the silicone fluid forms a liquid interface above the resin layer and prevents fauna and flora to attach firmly to the surface of the support. Such an antifouling coating has a phase shift and is not homogeneous. Also known is EP 1829943 which discloses an anti-fouling coating composed of a composition comprising an organopolysiloxane and paraffin or a silicone oil. The paraffin or silicone oil exudes on the surface of the film formed by the coating and contributes to the anti-fouling performance. Such an antifouling coating also has a phase shift and is not homogeneous.
Enfin, on connaît le document JP 08081524 qui décrit une composition antisalissure comprenant une émulsion de résine silicone et éventuellement une cire ou une émulsion à base d'huile. Toutefois, de telles compositions ne s'avèrent pas stables dans le temps .Finally, JP 08081524 discloses an anti-fouling composition comprising a silicone resin emulsion and optionally an oil-based wax or emulsion. However, such compositions do not prove stable over time.
Considérant ce qui précède, un problème que se propose de résoudre l'invention est de mettre en œuvre une nouvelle formulation d'un système de revêtement antisalissure destinée à être facilement appliquée à des supports immergés, apte à limiter aussi efficacement la fixation des organismes marins que les peintures contenant des biocides, étanche, stable dans le temps et homogène à une phase unique, et qui ne présente pas les effets indésirables observés dans l'art antérieur.Considering the above, a problem to be solved by the invention is to implement a new formulation of an anti-fouling coating system intended to be easily applied to submerged supports, able to limit the fixation of marine organisms as efficiently as possible. that the paints containing biocides, sealed, stable over time and homogeneous to a single phase, and which does not have the undesirable effects observed in the prior art.
Ainsi, dans l'optique de satisfaire ce besoin, la demanderesse a découvert, de manière inattendue, qu'une formulation aqueuse, hydrophobe et oléophobe, homogène à une phase unique, destinée à être appliquée à des supports présents dans un milieu aqueux, présente une remarquable activité antisalissure pour défavoriser la fixation des organismes marins, est étanche et stable dans le temps, procurant une nouvelle alternative, tout en respectant l'environnement et la santé humaine. La formulation selon l'invention offre notamment les avantages suivants par rapport à l'art antérieur :Thus, with a view to satisfying this need, the Applicant has unexpectedly discovered that an aqueous, hydrophobic and oleophobic, single-phase homogeneous formulation intended to be applied to supports present in an aqueous medium, presents a remarkable anti-fouling activity to disadvantage the fixation of marine organisms, is waterproof and stable over time, providing a new alternative, while respecting the environment and human health. The formulation according to the invention offers the following advantages in particular with respect to the prior art:
- la formulation ne contient pas de biocide toxique et ne présente pas les effets indésirables des peintures les contenant ; - la formulation est respectueuse de l'environnement ; - la formulation a un point éclair supérieur à 550C, et est considérée comme ininflammable ;- the formulation contains no toxic biocide and does not have the undesirable effects of the paints containing them; - the formulation is respectful of the environment; the formulation has a flash point greater than 55 ° C., and is considered as non-flammable;
- la formulation offre des avantages en termes de sécurité de transport, de stockage et d'utilisation ; la formulation est en phase aqueuse hydrophobe , oléophobe et homogène à une phase unique ;- the formulation offers advantages in terms of transport safety, storage and use; the formulation is in hydrophobic, oleophobic and homogeneous aqueous phase with a single phase;
- la formulation permet de protéger efficacement la partie immergée de tout support contre la fixation des organismes marins et de leurs éventuelles dégradations ; - la formulation limite l'introduction de pathogènes via les organismes marins avec le développement des transports maritimes ; la formulation est particulièrement adaptée pour une application sur les carènes de navire de sorte à diminuer le poids et la résistance à l'eau, à diminuer la trainée hydrodynamique, à augmenter la vitesse, à diminuer la consommation en carburant, et à diminuer la fréquence de nettoyage ;the formulation makes it possible to effectively protect the immersed part of any support against the fixation of marine organisms and their possible degradation; - the formulation limits the introduction of pathogens via marine organisms with the development of maritime transport; the formulation is particularly suitable for application on ship hulls so as to reduce weight and water resistance, reduce hydrodynamic drag, increase speed, decrease fuel consumption, and decrease frequency of cleaning ;
- la formulation s'applique sur une carène éventuellement revêtue d'un anticorrosif ;the formulation is applied to a hull optionally coated with an anticorrosive;
- la formulation sèche rapidement à température ambiante ; etthe formulation dries rapidly at room temperature; and
- la formulation est facilement nettoyable. L'invention a donc pour premier objet une formulation d'un système de revêtement antisalissure destinée à être appliquée à des supports immergés, caractérisée en ce qu'elle comprend au moins 30% en poids du poids total d'eau, au moins 10% en poids d'extrait sec du poids total d'un hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en mélange et au moins 5% en poids d'extrait sec du poids total d'un agent actif anti-adhérent.- the formulation is easily cleaned. The invention therefore firstly relates to a formulation of an anti-fouling coating system intended to be applied to immersed supports, characterized in that it comprises at least 30% by weight of the total weight of water, at least 10% by weight of dry extract of the total weight of a water repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight an anti-adherent active agent.
De plus, elle a pour deuxième objet un procédé de traitement de supports destinés à être immergés avec une formulation selon l'invention, caractérisé en ce que la formulation est appliquée en au moins une couche par pulvérisation, au rouleau ou au pinceau sur le support à protéger contre les salissures marines, après nettoyage et séchage préalable du support, à une température extérieure comprise entre environ 5° et environ 500C, préférentiellement entre environ 15° et environ 300C, puis est séchée à température ambiante, par exemple 230C, pendant environ 25 minutes et environ 40 minutes entre deux couches successives, et entre environ 30 minutes et environ 50 minutes avant la mise à l'eau. Enfin, elle a pour troisième objet l'utilisation d'une formulation selon l'invention, comme agent antisalissure destiné à défavoriser l'accroche des organismes marins tels que les algues, coquillages et autres crustacés sur tout support immergé et notamment les carènes des navires . L'invention et les avantages qui en découlent seront mieux compris à la lecture de la description et des modes de réalisation non limitatifs qui suivent.In addition, its second object is a process for treating substrates intended to be immersed with a formulation according to the invention, characterized in that the formulation is applied in at least one layer by spraying, with a roller or with a brush, on the support to be protected against marine fouling, after cleaning and prior drying of the support, at an outside temperature of between approximately 5 ° and approximately 50 ° C., preferably between approximately 15 ° and approximately 30 ° C. then is dried at room temperature, for example 23 0 C, for about 25 minutes and about 40 minutes between two successive layers, and between about 30 minutes and about 50 minutes before launching. Finally, it has the third object the use of a formulation according to the invention, as anti-fouling agent intended to disadvantage the grip of marine organisms such as algae, shells and other crustaceans on any submerged support including hulls of ships . The invention and the advantages thereof will be better understood on reading the description and the non-limiting embodiments that follow.
Dans cette description, à moins qu'il ne soit spécifié autrement, il est entendu que, lorsqu'un intervalle de concentration est donné, il inclut les bornes supérieures et inférieures dudit intervalle, et est donné en poids du poids total de la formulation.In this specification, unless otherwise specified, it is understood that, when a concentration range is given, it includes the upper and lower limits of said range, and is given by weight of the total weight of the formulation.
La formulation selon l'invention d'un système de revêtement antisalissure est destinée à être appliquée à des supports immergés .The formulation according to the invention of an anti-fouling coating system is intended to be applied to submerged supports.
A titre non limitatif de supports immergés, on peut citer tous les objets ou constructions destinés à être immergés dans un milieu marin tels que les carènes de bateaux ou de navires, les embases moteur, les hélices, les arbres d'hélices, les flotteurs, les piliers de quais ou de pontons, les bouées de balisage, ou encore tout matériel de mesure ou de prise de vue apte à être immergé .Non-limiting examples of submerged supports include all objects or constructions intended to be immersed in a marine environment such as hulls of boats or ships, engine bases, propellers, propeller shafts, floats, the piers of wharves or pontoons, buoys, or any measuring or shooting equipment suitable for being immersed.
Aussi, la formulation selon l'invention s'applique sur tout type de surface, par exemple le bois, tout métal, tel que par exemple l'aluminium et le fer, tout alliage de métaux tel que l'acier, le polyester, le verre, la faience, ou encore le béton.Also, the formulation according to the invention applies to any type of surface, for example wood, any metal, such as for example aluminum and iron, any metal alloy such as steel, polyester, glass, earthenware, or even concrete.
La formulation selon l'invention comprend au moins 30% en poids du poids total d'eau, au moins 10% en poids d'extrait sec du poids total d'un hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en mélange et au moins 5% en poids d'extrait sec du poids total d'un agent actif antiadhérent . La formulation selon l'invention comprend au moins 30% d' eau .The formulation according to the invention comprises at least 30% by weight of the total weight of water, at least 10% by weight of dry extract of the total weight of a water-repellent chosen from a silicone resin, a polyurethane resin and / or a acrylic styrene copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight of an antiadhesive active agent. The formulation according to the invention comprises at least 30% water.
Selon un mode de réalisation de l'invention, la formulation comprend au moins 50% d'un système solvant - co- solvant comprenant majoritairement de l'eau. Le système solvant - co-solvant selon l'invention comprend au moins un composé non aqueux choisi parmi les hydrocarbures, les alcools, les cétones, les esters, pris seul ou en combinaison.According to one embodiment of the invention, the formulation comprises at least 50% of a solvent-co-solvent system comprising predominantly water. The solvent-co-solvent system according to the invention comprises at least one non-aqueous compound chosen from hydrocarbons, alcohols, ketones and esters, taken alone or in combination.
Selon un exemple de réalisation d'une formulation selon l'invention, le système solvant - co-solvant comprend au moins 20% d'un composé non aqueux choisi parmi les hydrocarbures, les alcools, les cétones, les esters, pris seul ou en combinaison.According to an exemplary embodiment of a formulation according to the invention, the solvent-co-solvent system comprises at least 20% of a non-aqueous compound chosen from hydrocarbons, alcohols, ketones and esters, taken alone or in combination.
A titre d'exemples non limitatifs d'hydrocarbures selon l'invention, on peut citer les solvants hydrocarbonés ayant de 2 à 24 atomes de carbone, les hydrocarbures paraffiniques, isoparaffiniques, cycloparaffinique tel que le naphta lourd hydrotraité, et aromatiques tel que le xylène, préférentiellement un co-solvant naphta en C8 à ClO et un hydrocarbure aliphatique désaromatisé.By way of nonlimiting examples of hydrocarbons according to the invention, mention may be made of hydrocarbon solvents having 2 to 24 carbon atoms, paraffinic, isoparaffinic, cycloparaffinic hydrocarbons such as hydrotreated heavy naphtha, and aromatics such as xylene. , preferably a C8 to C10 naphtha co-solvent and a deflavored aliphatic hydrocarbon.
A titre d'exemples non limitatifs d'alcools selon l'invention, on peut citer un hydrocarbone alcoolique ayant de 2 à 20 atomes de carbone, de préférence l'éthanol, 1' isopropanol ou le butanol ou encore le monopropylène glycol . Le système solvant - co-solvant aqueux selon l'invention est ainsi hydroalcoolique. Le système solvant - co-solvant selon l'invention a avantageusement des propriétés antigel, conférée notamment par le monopropylène glycol .As non-limiting examples of alcohols according to the invention, mention may be made of an alcoholic hydrocarbon having 2 to 20 carbon atoms, preferably ethanol, isopropanol or butanol or else monopropylene glycol. The aqueous solvent-co-solvent system according to the invention is thus hydroalcoholic. The solvent-co-solvent system according to the invention advantageously has antifreeze properties, conferred in particular by monopropylene glycol.
A titre d'exemple non limitatif de cétones selon l'invention, on peut citer préfêrentiellement la N-méthyl pyrrolidone.As a nonlimiting example of ketones according to the invention, N-methyl pyrrolidone may be mentioned preferentially.
A titre d'exemples non limitatifs d'ester selon l'invention, on peut citer préfêrentiellement l'ester mêthylique de colza, encore plus préfêrentiellement un mélange d'oléate et de linoléate de méthyle.As non-limiting examples of the ester according to the invention, mention may preferably be made of rapeseed methyl ester, even more preferably a mixture of oleate and methyl linoleate.
Le système solvant - co-solvant aqueux utilisé selon l'invention est donc choisi de sorte à être apte et nécessaire pour obtenir un mélange homogène à une phase unique avec 1 ' hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en mélange et l'agent actif anti-adhérent.The aqueous solvent-co-solvent system used according to the invention is therefore chosen so as to be suitable and necessary to obtain a homogeneous mixture with a single phase with one of the water-repellent chosen from a silicone resin, a polyurethane resin and / or a resin. acrylic styrene copolymer, taken alone or in admixture and the antiadhesive active agent.
Selon un exemple de réalisation d'une formulation selon l'invention, le co-solvant non aqueux est choisi parmi les solvants de classe 3 qui sont non inflammables à température ambiante, avec un point éclair supérieur à 550C.According to an exemplary embodiment of a formulation according to the invention, the non-aqueous co-solvent is chosen from solvents of class 3 which are non-flammable at ambient temperature, with a flash point greater than 55 ° C.
A titre d'exemple non limitatif de co-solvant non aqueux de classe 3, on peut citer la N-méthyl pyrrolidone.By way of non-limiting example of a non-aqueous co-solvent of class 3, mention may be made of N-methyl pyrrolidone.
Un tel co-solvant non aqueux utilisé selon l'invention est donc choisi de sorte à être apte et nécessaire pour obtenir un mélange homogène à une phase unique avec l' hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, et l'agent actif anti- adhérent en les solubilisant, pour favoriser l'effet d'anti- accroche sur le support immergé et pour obtenir une formulation ayant un point éclair supérieur à 550C.Such a non-aqueous co-solvent used according to the invention is therefore chosen so as to be suitable and necessary to obtain a homogeneous mixture at a single phase with the water-repellent chosen from a silicone resin, a polyurethane resin and / or a copolymer resin. acrylic styrene, and the anti-adherent active agent by solubilizing them, to promote the anti-adhesion effect on the immersed support and to obtain a formulation having a flash point greater than 55 ° C.
Selon un exemple de réalisation de l'invention, la formulation comprend un système solvant - co-solvant comprenant essentiellement de l'eau, soit au moins 80% en poids du poids du système solvant - co-solvant d'eau. Selon un exemple de réalisation de l'invention, la formulation comprend au moins 50% en poids du poids total d' eau.According to an exemplary embodiment of the invention, the formulation comprises a solvent-co-solvent system essentially comprising water, ie at least 80% by weight of the weight of the solvent-water co-solvent system. According to an exemplary embodiment of the invention, the formulation comprises at least 50% by weight of the total weight of water.
La formulation selon l'invention comprend également au moins 10% en poids d'extrait sec du poids total d'un hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en mélange.The formulation according to the invention also comprises at least 10% by weight of dry extract of the total weight of a water-repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture.
La quantité d' hydrofugeant choisi parmi une résine silicone, polyuréthane et/ou copolymère styrène acrylique, prise seule ou en mélange, et en particulier pour la résine silicone ou polyuréthane, est avantageusement considérée en phase aqueuse ou solvantée. La formulation selon l'invention peut comprendre ainsi moins de 10% d' hydrofugeant à base de résine silicone ou de résine polyuréthane ou de résine copolymère styrène acrylique considérée indépendamment l'une de l'autre en poids d'extrait sec du poids total, le mélange de deux types de résines ou des trois types de résines étant au moins de 10% en poids d'extrait sec du poids total de la formulation.The amount of water-repellent chosen from a silicone resin, polyurethane resin and / or acrylic styrene copolymer, taken alone or as a mixture, and in particular for the silicone or polyurethane resin, is advantageously considered in the aqueous or solvent phase. The formulation according to the invention may thus comprise less than 10% of silicone resin-based water repellant or of polyurethane resin or acrylic styrene copolymer resin considered independently of one another by weight of dry extract of the total weight, the mixture of two types of resins or of the three types of resins being at least 10% by weight of dry extract of the total weight of the formulation.
L'hydrofugeant à base de résine silicone selon l'invention est une résine siloxane, polysiloxane et/ou leurs dérivés, prise seule ou en mélange, en phase aqueuse ou solvantée, de préférence en phase aqueuse, non ionique. A titre d'exemples non limitatifs de résine silicone selon l'invention, on peut citer préférentiellement la résine polyméthylsiloxane ou polydiméthylsiloxane, en phase aqueuse ou solvantée .The waterproofing agent based on silicone resin according to the invention is a siloxane resin, polysiloxane and / or their derivatives, taken alone or as a mixture, in the aqueous phase or in the solvent phase, preferably in the aqueous, nonionic phase. By way of nonlimiting examples of silicone resin according to the invention, mention may preferably be made of polymethylsiloxane or polydimethylsiloxane resin, in aqueous or solvent phase.
L'hydrofugeant à base de résine silicone, polyuréthane et/ou copolymère styrène acrylique selon l'invention, hydrophobe, est choisi de sorte à permettre la cohésion du film de revêtement antisalissure sur son support.The waterproofing agent based on silicone resin, polyurethane and / or styrene acrylic copolymer according to the invention, hydrophobic, is chosen so as to allow the cohesion of the anti-fouling coating film on its support.
Selon un exemple de réalisation d'une formulation selon l'invention, l ' hydrofugeant selon l'invention est un mélange d'environ 2% d'une solution de résine polyméthylsiloxane à 70% de matière active en phase solvantée ou 44 à 50% en phase aqueuse, de préférence en phase aqueuse, et d'environ 12% d'une résine polyméthylsiloxane en émulsion aqueuse ou solvantée, de préférence en émulsion aqueuse.According to an exemplary embodiment of a formulation according to the invention, the water-repellent according to the invention is a mixture of about 2% of a solution of polymethylsiloxane resin with 70% of active material in the solvent phase or 44 to 50% phase aqueous, preferably in aqueous phase, and about 12% of a polymethylsiloxane resin in aqueous or solvent emulsion, preferably in aqueous emulsion.
Avantageusement, l ' hydrofugeant à base de résine silicone est une résine polyméthylsiloxane en émulsion aqueuse non ionique. Préfêrentiellement, la résine polyméthylsiloxane est à 40% en poids d'extrait sec et comprend ainsi environ 60% d'eau.Advantageously, the waterproofing agent based on silicone resin is a polymethylsiloxane resin in aqueous nonionic emulsion. Preferably, the polymethylsiloxane resin is 40% by weight of solids and thus comprises about 60% water.
Selon un autre exemple de réalisation d'une formulation selon l'invention, l ' hydrofugeant est une résine polyuréthane, préfêrentiellement en émulsion aqueuse, encore plus préfêrentiellement à 50% en poids d'extrait sec et ainsi environ 50% d'eau ou encore à 35% en poids d'extrait sec, prise seule ou en combinaison avec une résine copolymère styrène acrylique et/ou une résine silicone, préfêrentiellement en émulsion aqueuse, par exemple à 40% en poids d'extrait sec.According to another embodiment of a formulation according to the invention, the water-repellent is a polyurethane resin, preferably in aqueous emulsion, even more preferably at 50% by weight of dry extract and thus about 50% of water or at 35% by weight of dry extract, taken alone or in combination with a styrene-acrylic copolymer resin and / or a silicone resin, preferably in aqueous emulsion, for example at 40% by weight of solids.
Selon un autre exemple de réalisation d'une formulation selon l'invention, l ' hydrofugeant est encore plus préférentiellement une résine copolymère styrène acrylique prise seule.According to another embodiment of a formulation according to the invention, the water-repellent is even more preferably a styrene acrylic copolymer resin taken alone.
Un tel hydrofugeant , hydrophobe, à base de résine polyuréthane et/ou copolymère styrène acrylique utilisé selon l'invention est donc choisi de sorte à favoriser l'adhérence entre le support, revêtu éventuellement d'une couche primaire d'accroché ou d'une couche anticorrosion, et la couche de revêtement antisalissure et également entre les différentes couches de revêtement antisalissure, et à augmenter également la résistance à l'eau. La formulation selon l'invention comprend également au moins 5% en poids d'extrait sec du poids total d'un agent actif anti-adhérent .Such hydrophobic water-repellent, based on polyurethane resin and / or acrylic styrene copolymer used according to the invention is thus chosen so as to promote adhesion between the support, optionally coated with a primary layer of hooked or a anticorrosive layer, and the anti-fouling coating layer and also between the different layers of antifouling coating, and also increase the water resistance. The formulation according to the invention also comprises at least 5% by weight of dry extract of the total weight of an anti-adherent active agent.
La quantité d'agent actif anti-adhérent est avantageusement considérée en phase aqueuse ou solvantée, préférentiellement aqueuse. La formulation selon l'invention comprend ainsi au moins environ 5% en poids d'extrait sec d'agent actif anti-adhérent du poids total. La formulation peut comprendre environ 10%, environ 15% ou environ 20% d'extrait sec d'agent actif anti-adhérent du poids total.The amount of antiadhesive active agent is advantageously considered in aqueous or solvent phase, preferably aqueous. The formulation according to the invention thus comprises at least about 5% by weight of dry extract of anti-adherent active agent of the total weight. The formulation may comprise about 10%, about 15% or about 20% dry extract of antiadhesive active agent of the total weight.
L'agent actif anti-adhérent selon l'invention est choisi parmi des composés gras tels que les cires, graisses ou paraffines, naturelles ou synthétiques, ayant un point de goutte compris entre 30° et 1000C.The antiadhering active agent according to the invention is chosen from fatty compounds such as waxes, fats or paraffins, natural or synthetic, having a dropping point of between 30 ° and 100 ° C.
L'agent actif anti-adhérent selon l'invention peut se présenter sous forme solide, par exemple de poudre ou de pastilles, visqueuse ou liquide, préférentiellement sous forme de dispersion ou d'émulsion aqueuse.The antiadhering active agent according to the invention may be in solid form, for example powder or pellets, viscous or liquid, preferably in the form of dispersion or aqueous emulsion.
Une telle dispersion ou émulsion aqueuse d'agent actif anti-adhérent permet de solubiliser l'agent actif antiadhérent et d'éviter les phénomènes de déphasage dans la formulation selon l'invention.Such an aqueous dispersion or emulsion of antiadhesive active agent makes it possible to solubilize the antiadhesive active agent and to avoid phase shift phenomena in the formulation according to the invention.
A titre d'exemples non limitatifs de cires, on peut citer la cire de carnauba, d'origine végétale, ayant un point de fusion compris entre 78° et 85°C, l'un des plus hauts parmi les cires d'origine naturelles et une dureté très élevée, et la cire d'abeille ayant un point de fusion de 640C.By way of non-limiting examples of waxes, mention may be made of carnauba wax, of plant origin, having a melting point of between 78 ° and 85 ° C., one of the highest of the waxes of natural origin. and a very high hardness, and beeswax having a melting point of 64 ° C.
A titre d'exemple non limitatif de graisse, on peut citer la lanoline, d'origine animale obtenue par purification et raffinage du suint.By way of non-limiting example of fat, mention may be made of lanolin, of animal origin obtained by purification and refining of the suint.
Préférentiellement, l'agent actif anti-adhérent selon l'invention est une paraffine, encore plus préférentiellement une paraffine 56/58, c'est-à-dire ayant un point de goutte à environ 56 -580C.Preferably, the antiadhering active agent according to the invention is a paraffin, even more preferably a paraffin 56/58, that is to say having a drop point at about 56 -58 0 C.
Selon un exemple de réalisation de l'invention, la formulation comprend environ 20% en poids d'extrait sec d'agent actif anti-adhérent et environ 40% lorsqu'il est en émulsion aqueuse à 50%.According to an exemplary embodiment of the invention, the formulation comprises about 20% by weight of dry extract of antiadhesive active agent and about 40% when it is in aqueous emulsion at 50%.
Il est difficile d'obtenir un mélange homogène à une phase unique en présence d'une grande quantité, par exemple au moinsIt is difficult to obtain a single-phase homogeneous mixture in the presence of a large quantity, for example at least
5% d'extrait sec d'un agent hydrophobe et oléophobe tel que la paraffine, par exemple 15% de paraffine, seule ou prise en combinaison avec au moins 10% d'un hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en combinaison. De plus, la paraffine en tant qu'agent anti-adhésion est connue pour ses problèmes de faible cohésion entre les couches successivement déposées et nécessite la mise en œuvre d'adjuvants spécifiques pour surmonter ce problème. Il est également difficile de faire adhérer un tel corps gras comme la paraffine sur un support. Aussi, la combinaison de solvant - co-solvant utilisée dans la formulation selon l'invention, comprenant majoritairement de l'eau, permet l'obtention d'une formulation homogène à une phase unique. La formulation selon l'invention est ainsi homogène, à une phase unique, avant et après application, et stable dans le temps. En effet, ce système de solvant - co-solvant aqueux dilue et solubilise les composés hydrophobes de sorte à pouvoir appliquer, après agitation, une ou plusieurs couches homogènes à la surface du support à traiter, apte à être immergé. Le revêtement antisalissure ainsi obtenu après application forme une couche solide, homogène, à une phase unique. Selon un exemple de réalisation de l'invention, l'utilisation d'une faible teneur en co-solvant non aqueux, inférieure à 5% en poids du poids total, tel que la N-méthyl pyrrolidone, prise seule ou en combinaison avec de l'ethanol, permet d'obtenir un mélange parfaitement homogène à une phase unique avec l ' hydrofugeant et l'agent actif anti-adhérent , stable, sans phénomène de déphasage au cours du temps. La N- méthyl pyrrolidone qui est un agent coalescent permet également d'aider à la formation du film de revêtement antisalissure et l'ethanol d'accélérer les temps de séchage. Avantageusement, la formulation selon l'invention a un point éclair supérieur à 550C, notamment par le choix d'un système solvant - co-solvant adapté comprenant essentiellement de l'eau et d'un co-solvant comprenant de l'ester méthylique de colza, mélange d'oléate et de linoléate de méthyle, ou d'un mélange de naphta en C8 à ClO et d'un hydrocarbure aliphatique désaromatisé, ou encore d'un système solvant - co-solvant comprenant essentiellement de l'eau, par exemple au moins 80% en poids du poids du système solvant - co-solvant, et éventuellement d'une faible quantité de N-méthyl pyrrolidone, inférieure à 5%, prise seule ou en combinaison. La formulation est ainsi considérée comme ininflammable.5% of dry extract of a hydrophobic and oleophobic agent such as paraffin, for example 15% of paraffin, alone or in combination with at least 10% of a water-repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or in combination. In addition, paraffin as an anti-adhesion agent is known for its problems of low cohesion between the layers deposited successively and requires the implementation of specific adjuvants to overcome this problem. It is also difficult to adhere such a fatty substance as paraffin on a support. Also, the combination of solvent-co-solvent used in the formulation according to the invention, mainly comprising water, makes it possible to obtain a homogeneous formulation with a single phase. The formulation according to the invention is thus homogeneous, in a single phase, before and after application, and stable over time. Indeed, this aqueous solvent-co-solvent system dilutes and solubilizes the hydrophobic compounds so that, after stirring, one or more homogeneous layers can be applied to the surface of the support to be treated, capable of being immersed. The anti-fouling coating thus obtained after application forms a solid, homogeneous layer with a single phase. According to an exemplary embodiment of the invention, the use of a low content of non-aqueous co-solvent, less than 5% by weight of the total weight, such as N-methyl pyrrolidone, taken alone or in combination with ethanol, allows to obtain a perfectly homogeneous mixture at a single phase with the water repellent and the active anti-adherent agent, stable, without phase shift phenomenon over time. N-methyl pyrrolidone which is a coalescing agent also helps to form the antifouling coating film and ethanol to accelerate the drying times. Advantageously, the formulation according to the invention has a flash point greater than 55 ° C., in particular by choosing a suitable solvent-co-solvent system essentially comprising water and a co-solvent comprising ester. rapeseed methyl, a mixture of oleate and methyl linoleate, or a mixture of C8 to ClO naphtha and a deflated aliphatic hydrocarbon, or a solvent-co-solvent system comprising essentially water, for example at least 80% by weight of the solvent-co-solvent system, and optionally a small amount of N-methyl pyrrolidone, less than 5%, taken alone or in combination. The formulation is thus considered as nonflammable.
La formulation selon l'invention ininflammable et non toxique, offre des avantages en termes de sécurité de transport, de stockage et d'utilisation, ne requérant pas de précautions particulières adaptées . Avantageusement, la formulation selon l'invention comprend également un agent répulsif non toxique, naturel, apte à repousser l'accroche en particulier des algues, et autres organismes marins et crustacés, sur la surface immergée à protéger. On peut citer à titre d'exemples non limitatifs d'agent répulsif, des huiles essentielles par exemple de menthol, de camphre, d'arbre à thé, de géranium, de thym, de laurier, de l'essence de poivre ou encore des extraits de pépins de pamplemousse . Avantageusement l'agent non toxique, naturel, apte à repousser l'accroche en particulier des algues, est composé de souches bactériennes a une concentration inférieure à 5% en poids du poids total, préférentiellement entre 0,1 et 0,5%.The formulation according to the invention non-flammable and non-toxic, offers advantages in terms of safety of transport, storage and use, not requiring special precautions adapted. Advantageously, the formulation according to the invention also comprises a non-toxic repellent agent, natural, able to repel the grip especially of algae, and other marine organisms and crustaceans, on the immersed surface to be protected. Non-limiting examples of repellent agents that may be mentioned include essential oils, for example menthol, camphor, tea tree, geranium, thyme, bay leaf, peppermint oil, or the like. Grapefruit seed extracts. Advantageously, the non-toxic agent, natural, able to repel the grip especially of algae, is composed of bacterial strains at a concentration of less than 5% by weight of the total weight, preferably between 0.1 and 0.5%.
On peut citer à titre d'exemple des produits algicides écologiques. De tels produits sont parfaitement miscibles en solution aqueuse, conservent leurs propriétés dans la mesure où ils ne sont pas dégradés par des solvants organiques inadaptés et permettent de conserver une formulation selon l'invention homogène avant et après application. La formulation selon l'invention est susceptible également de comprendre les constituants suivants : de l'oxyde de silice et/ou du talc qui donne de la dureté et répartit l'agent actif anti-adhérent dans le film sec en plus de le stabiliser dans le revêtement antisalissure liquide ; un tensio-actif , apte à empêcher le déphasage et à permettre la miscibilité entre l'eau et les différents solvants et co-solvants, et permettant notamment la dispersion de la silice, et/ou du talc et de la cire de paraffine, de préférence un agent polymère de couplage mouillant de type hydrophile et hypophile, hydrosoluble , non ionique, préférentiellement l'octylphénol éthoxylé comprenant environ 11 moles d'oxyde d'éthylène ou un agent à base de polymère d'acrylate de sodium ou un tensioactif anionique ; un épaississant, de préférence un polyuréthane liquide en solution aqueuse, ou un épaississant acrylique qui sont des agents rhéologiques permettant de régler la rhéologie pour une application optimale au pinceau, à la brosse ou au rouleau ; un agent anti corrosion ; un agent anti mousse ; et un ou plusieurs colorants organiques, naturels ou synthétiques, ou encore tout pigment organique ou minéral (inorganique) . A titre d'exemples non limitatif de colorant, on peut citer l'iron chromium hématite (marron), le cobalt chromite green spinel (vert) , le cobalt aluminate spinel (bleu) , le copper chrome black spinel (noir) , le dioxyde de titane (blanc), insolubles en phase aqueuse.For example, ecological algicidal products may be mentioned. Such products are perfectly miscible in aqueous solution, retain their properties insofar as they are not degraded by unsuitable organic solvents and make it possible to maintain a formulation according to the homogeneous invention before and after application. The formulation according to the invention is also capable of comprising the following constituents: silica oxide and / or talc which gives hardness and distributes the antiadhesive active agent in the dry film in addition to stabilizing it in the liquid anti-fouling coating; a surfactant, able to prevent phase shift and to allow miscibility between water and the various solvents and co-solvents, and in particular allowing the dispersion of silica, and / or talc and paraffin wax, preferably a water-soluble, non-ionic, water-soluble hydrophilic and hypophile wetting coupling agent, preferably ethoxylated octylphenol comprising about 11 moles of ethylene oxide or a sodium acrylate polymer-based agent or an anionic surfactant; a thickener, preferably a liquid polyurethane in aqueous solution, or an acrylic thickener which are rheological agents for adjusting the rheology for optimum application by brush, brush or roller; an anti-corrosion agent; an anti-foam agent; and one or more organic, natural or synthetic dyes, or any organic or mineral (inorganic) pigment. By way of nonlimiting examples of dye, mention may be made of iron chromium hematite (brown), cobalt chromite green spinel (green), cobalt aluminate spinel (blue), copper chromium black spinel (black), dioxide Titanium (white), insoluble in aqueous phase.
L'utilisation de pigments minéraux, inorganiques, insolubles en phase aqueuse, confère avantageusement une opacité à la formulation à appliquer de sorte à modifier l'aspect extérieur de la surface du support à traiter.The use of inorganic, inorganic pigments, insoluble in the aqueous phase, advantageously confers an opacity to the formulation to be applied so as to modify the external appearance of the surface of the support to be treated.
La formulation selon l'invention peut également comprendre de manière facultative des traces d'un biocide tel que la chloro-méthyl-isothiazoline, qui est un conservateur anti moisissure destiné à la protection de la formulation lors de son stockage, par exemple dans un pot. Par traces, on entend une concentration inférieure ou égale à 0,01%. Avantageusement, la formulation ne contient aucune trace de biocide . A titre d'exemples de procédé de préparation d'un système de revêtement antisalissure selon l'invention, on réalise les étapes suivantes selon lesquelles :The formulation according to the invention may also optionally include traces of a biocide such as chloromethyl isothiazoline, which is an anti-mold preservative for the protection of the formulation during its storage, for example in a pot . By traces is meant a concentration less than or equal to 0.01%. Advantageously, the formulation contains no trace of biocide. As examples of a process for preparing an anti-fouling coating system according to the invention, the following steps are carried out according to which:
- on ajoute l'agent mouillant dans l'eau sous agitation lente ;the wetting agent is added to the water with slow stirring;
- on imbibe éventuellement la poudre d'oxyde de silice et/ou de talc avec un agent répulsif tel qu'une huile essentielle ou un composé de souches bactériennes ;the silica oxide powder and / or talc powder are optionally impregnated with a repellent agent such as an essential oil or a compound of bacterial strains;
- on dissout, sous agitation lente, la poudre d'oxyde de silice et/ou de talc éventuellement imbibée dans la phase liquide ; on rajoute ensuite successivement, toujours sous agitation lente, dans la phase liquide ainsi obtenue les composés dans l'ordre suivant : l ' hydrofugeant choisi parmi une résine polyuréthane en émulsion aqueuse, une résine polyméthylsiloxane en émulsion aqueuse également et/ou une résine copolymère styrène acrylique, prise seule ou en mélange, puis la cire de paraffine par exemple en émulsion aqueuse, et le co-solvant non aqueux tel que la N-méthyl pyrrolidone, ou un mélange d'hydrocarbures ; enfin, on ajuste la rhéologie avec un ou plusieurs épaississants de sorte à obtenir l'aspect souhaité pour la formulation ayant une densité, par exemple de 1,01, et une viscosité, par exemple Brookfield de 1,8 dPa.s à 230C ou cône plate de 0,4 dPa.s à 25°C.- Dissolving, with slow stirring, the powder of silica and / or talc oxide optionally imbibed in the liquid phase; is then added successively, still with slow stirring, in the liquid phase thus obtained the compounds in the following order: the water-repellent chosen from an aqueous emulsion polyurethane resin, a polymethylsiloxane resin also aqueous emulsion and / or a styrene copolymer resin acrylic, taken alone or in a mixture, then paraffin wax for example in aqueous emulsion, and non-aqueous co-solvent such as N-methyl pyrrolidone, or a mixture of hydrocarbons; finally, the rheology is adjusted with one or more thickeners so as to obtain the desired appearance for the formulation having a density, for example of 1.01, and a viscosity, for example Brookfield of 1.8 dPa.s at 23 ° C. C or flat cone 0.4 dPa.s at 25 ° C.
Selon un procédé alternatif de préparation d'un système de revêtement antisalissure selon l'invention, on réalise les étapes suivantes selon lesquelles :According to an alternative method of preparing an anti-fouling coating system according to the invention, the following steps are carried out according to which:
- on dissout l'agent actif anti-adhérent, par exemple la paraffine, dans les solvants et co- solvants utilisés selon l'invention, l'ester méthylique de colza, mélange d'oléate et de linoléate de méthyle, excepté l'eau. Cette dissolution est réalisée sous agitation puissante ;the active anti-adherent agent, for example paraffin, is dissolved in the solvents and co-solvents used according to the invention, the methyl ester of rapeseed, a mixture of oleate and methyl linoleate, except for water; . This dissolution is carried out with powerful stirring;
- on rajoute ensuite dans la phase liquide obtenue les composés dans l'ordre suivant : une première partie dethe compounds obtained in the following order are then added to the liquid phase obtained: a first part of
1 ' hydrofugeant , par exemple la solution de résine polymêthylsiloxane à 70% de matière active en phase solvantée, l'épaississant, la seconde partie de l ' hydrofugeant , par exemple la résine polymêthylsiloxane en émulsion aqueuse, l'antigel, puis le biocide ; - puis, on rajoute le tensioactif, par exemple l'octylphénol éthoxylé ;1 'water repellent, for example the resin solution polymethylsiloxane containing 70% of active material in the solvent phase, the thickener, the second part of the water-repellent, for example the polymethylsiloxane resin in aqueous emulsion, the antifreeze and then the biocide; then, the surfactant is added, for example octylphenol ethoxylated;
- enfin, on rajoute l'eau de sorte à obtenir une phase homogène à une phase unique, stable dans le temps.- Finally, we add the water so as to obtain a homogeneous phase to a single phase, stable over time.
Suivant la teinte désirée du revêtement antisalissure selon l'invention, on peut ajouter également au final un colorant , par exemple un pigment inorganique .Depending on the desired color of the antifouling coating according to the invention, it is also possible to add a dye, for example an inorganic pigment.
Les techniques et les temps de mélange sont connus de l'homme de l'art et sont adaptés aux quantités utilisées.The techniques and mixing times are known to those skilled in the art and are adapted to the quantities used.
La formulation selon l'invention se présente avantageusement sous forme liquide,' sous forme d' émulsion ou encore sous forme de gel. La formulation selon l'invention est conditionnée dans tout récipient apte à recevoir un liquide ou un gel, tel que par exemple un pot.The formulation according to the invention is advantageously in liquid form, 'the form of an emulsion or gel form. The formulation according to the invention is packaged in any container capable of receiving a liquid or a gel, such as for example a pot.
Lors de son utilisation, la formulation peut être avantageusement agitée avant chaque application de sorte à obtenir un mélange parfaitement homogène en une phase unique .In use, the formulation can be advantageously stirred before each application so as to obtain a perfectly homogeneous mixture in a single phase.
La formulation est appliquée préférentiellement sur des surfaces lisses, mêmes peintes par exemple avec une peinture antisalissure à matrice dure ou à matrice érodable ou à matrice semi-érodable ou préalablement recouvertes d'un anticorrosif, préalablement nettoyées et séchées.The formulation is preferably applied to smooth surfaces, even painted for example with a hard-matrix or erodible matrix antifouling paint or semi-erodible matrix or previously coated with an anticorrosive, previously cleaned and dried.
La formulation est appliquée en au moins une couche par pulvérisation au pistolet électrique ou avec un pulvérisateur manuel, au rouleau ou au pinceau, ou encore avec un chiffon, sur le support à protéger contre les salissures marines .The formulation is applied in at least one layer by spraying with an electric spray gun or with a manual sprayer, roller or brush, or with a cloth, on the support to be protected against marine fouling.
Préférentiellement, la formulation est appliquée en effectuant des mouvements croisés, horizontaux et verticaux, de manière à traiter et humidifier le support sans recharger les endroits déjà traités. Avantageusement, la formulation s'applique en couche très mince . A titre d'exemple, un litre suffit à traiter environ 8 à 10 m2, voire 12 m2 avec une couche, par exemple une couche de 7,7 m2, soit une couche d'environ 120 μm humide d'épaisseur, lors d'une application au pinceau et de 11,3 m2, soit une couche d'environ 90 μm humide d'épaisseur, lors d'une application au rouleau laqueur.Preferably, the formulation is applied by carrying out cross-movements, horizontal and vertical, so as to treat and moisten the support without reloading the already treated areas. Advantageously, the formulation is applied in a very thin layer. For example, one liter is sufficient to treat about 8 to 10 m 2 , or 12 m 2 with a layer, for example a layer of 7.7 m 2 , a layer of about 120 microns wet thickness, when applied with a brush and 11.3 m 2 , or a layer of about 90 microns wet thickness, during an application to the lacquer roller.
La formulation est appliquée de préférence dans un endroit sec, à une température extérieure comprise entre environ 5° et environ 5O0C, prëférentiellement entre environ 15° et environ 300C. Après application, on laisse sécher à température ambiante, par exemple 230C, pendant environ 25 minutes et environ 40 minutes entre deux couches successives, et entre environ 30 minutes et environ 50 minutes avant la mise à l'eau après application de la dernière couche. Les outils ayant servi à l'application de la formulation selon l'invention sont alors facilement nettoyables à l'eau et un tel nettoyage n'induit aucun risque de pollution. La formulation selon l'invention est sans risque de toxicité pour l'utilisateur et facilement utilisable, l'utilisateur ne nécessitant aucune protection particulière.The formulation is preferably applied in a dry place, at an outside temperature of between approximately 5 ° and approximately 50 ° C., preferably between approximately 15 ° and approximately 30 ° C. After application, it is allowed to dry at room temperature, for example 23 ° C. 0 C, for about 25 minutes and about 40 minutes between two successive layers, and between about 30 minutes and about 50 minutes before launching after applying the last layer. The tools used to apply the formulation according to the invention are then easily cleaned with water and such cleaning does not induce any risk of pollution. The formulation according to the invention is without risk of toxicity to the user and easy to use, the user does not require any particular protection.
La formulation selon l'invention, de par la teneur en eau d'au moins 30% en poids du poids total de la formulation permet d'obtenir un revêtement antisalissure qui ne se décolle pas lors de son application. En effet, dans le cas de l'utilisation sur des supports imparfaitement secs de solvants organiques dans des compositions de revêtements antisalissure, l'humidité emprisonnée entre le support et la couche de revêtement conduit inévitablement à une mauvaise adhérence, au décollement du revêtement et à l'attaque et la dégradation du support, les solvants s 'évaporant plus rapidement que l'eau lors du séchage. En revanche, la formulation aqueuse selon l'invention peut être appliquée sur un support imparfaitement sec de par l' évaporation de l'eau emprisonnée sous le revêtement lors du séchage simultanément à l' évaporation de l'eau comprise dans la formulation. On obtient après application d'une formulation selon l'invention un revêtement antisalissure étanche qui ne réabsorbe pas d'eau lors de l'immersion du support traité. Aussi, lors du séchage, l'agent actif anti-adhérent, devient solide et forme avec le reste de la formulation une couche adhérente, homogène, solide et sèche. L'agent anti-adhérent n'est ainsi pas exsudé en surface de la couche de revêtement antisalissure obtenue selon l' invention.The formulation according to the invention, by the water content of at least 30% by weight of the total weight of the formulation provides an antifouling coating that does not peel off during its application. Indeed, in the case of use on imperfectly dry substrates of organic solvents in antifouling coating compositions, moisture trapped between the support and the coating layer inevitably leads to poor adhesion, detachment of the coating and attack and degradation of the support, solvents evaporating faster than water during drying. In contrast, the aqueous formulation according to the invention can be applied to an imperfectly dry support by evaporation of the water trapped under the coating during drying simultaneously with the evaporation of the water included in the formulation. After application of a formulation according to the invention, a coating is obtained waterproof anti-fouling which does not reabsorb water during the immersion of the treated support. Also, during drying, the antiadhesive active agent becomes solid and forms with the rest of the formulation an adherent, homogeneous, solid and dry layer. The release agent is thus not exuded on the surface of the antifouling coating layer obtained according to the invention.
A titre d'exemple, un essai réalisé avec application d'une couche de la formulation selon l'invention de 100 μm humide d'épaisseur sur du verre et après mesure au BK drying recorder à vitesse adaptée, a mis en évidence une évaporation des solvants après 6 min, un temps de séchage en surface du revêtement selon l'invention après 10 min, un début de séchage à cœur après 39 min et un séchage total après 47 min, dans des conditions standard de séchage à température ambiante .By way of example, a test carried out with application of a layer of the formulation according to the invention of 100 μm wet thickness on glass and after measurement with the BK drying recorder at a suitable speed, evidenced evaporation of solvents after 6 min, a surface drying time of the coating according to the invention after 10 min, a start of core drying after 39 min and a total drying after 47 min, under standard drying conditions at room temperature.
Pour une application optimale de la formulation selon l'invention, on applique préférentiellement trois couches lors de la première utilisation.For optimal application of the formulation according to the invention, three layers are preferably applied during the first use.
La durée de vie du traitement est de douze mois en milieu marin, un stationnement prolongé hors de l'eau n'ayant pas d'incidence sur l'efficacité du traitement.The life of the treatment is 12 months in the marine environment, prolonged parking outside the water does not affect the effectiveness of the treatment.
Selon un mode de réalisation alternatif de l'invention, la formulation ne contient pas de pigment ou de colorant, et ne change pas la couleur du support après application. La formulation selon l'invention est résistante à l'abrasion. Par exemple, un premier test réalisé avec application d'une couche de la formulation selon l'exemple 1 de l'invention de 150 μm humide d'épaisseur sur un primaire d'accrochage de 150 μm d'épaisseur, et après un séchage accéléré de 48h aux conditions standards suivie de 48h dans une enceinte à 400C, après 200 cycles de frottement, a mis en évidence une perte moyenne d'épaisseur de film de revêtement antisalissure selon l'invention de 16 μm. Un second test réalisé avec application d'une couche de la formulation selon l'exemple 1 de l'invention de 150 μm humide d'épaisseur sur un primaire d'accrochage, et après un séchage de trois semaines aux conditions normalisées, après 200 cycles de frottement, a mis en évidence une perte moyenne d'épaisseur de film de revêtement antisalissure selon l'invention de 12 μm.According to an alternative embodiment of the invention, the formulation does not contain pigment or dye, and does not change the color of the support after application. The formulation according to the invention is resistant to abrasion. For example, a first test carried out with application of a layer of the formulation according to Example 1 of the invention of 150 microns wet thickness on a primer of 150 microns thick, and after accelerated drying 48h at standard conditions followed by 48h in a chamber at 40 0 C, after 200 cycles of friction, has demonstrated a mean loss of antifouling coating film thickness according to the invention of 16 microns. A second test carried out with the application of a layer of the formulation according to Example 1 of the invention of 150 μm wet thickness on a primer, and after drying for three weeks under normalized conditions, after 200 cycles of friction, demonstrated a mean thickness loss of antifouling coating film according to the invention of 12 microns.
Avantageusement, le traitement est renouvelé chaque année, par application de deux nouvelles couches de la formulation selon l ' invention .Advantageously, the treatment is renewed each year, by application of two new layers of the formulation according to the invention.
La formulation selon l'invention forme, après application, une couche de revêtement antisalissure destinée à défavoriser l'accroche des organismes marins tels que les algues, coquillages et autres crustacés sur les supports immergés traités .The formulation according to the invention forms, after application, an anti-fouling coating layer intended to disadvantage the adhesion of marine organisms such as algae, shells and other crustaceans on the treated submerged supports.
En effet, la formulation rend la surface d'accrochage très lisse et facilite leur décrochement rapide soit par un simple nettoyage, sans avoir à gratter ou à faire le moindre effort, et même simplement lors du déplacement du navire par exemple.Indeed, the formulation makes the gripping surface very smooth and facilitates their quick release either by a simple cleaning, without having to scratch or to make the slightest effort, and even simply when moving the ship for example.
Ainsi, à titre d'exemple, un navire naviguant régulièrement conservera sa carène propre par le simple frottement de l ' eau sur la carène . Un navire ne naviguant pas régulièrement, grâce aux propriétés techniques de la formulation, s' auto nettoiera en naviguant et ne nécessite de ce fait pas de nettoyage spécifique contraignant.Thus, for example, a vessel sailing regularly will keep its own hull by the simple friction of the water on the hull. A ship not sailing regularly, thanks to the technical properties of the formulation, self cleans while sailing and therefore does not require specific cleaning binding.
A titre d'exemple, une coque lisse ainsi traitée avec la formulation selon l'invention offre moins de résistance à l'avancement, un tel traitement permettant de diminuer la trainée hydrodynamique, d'augmenter la vitesse et de réduire la consommation de carburant. En effet, 1 à 2 mm d'algues et organismes fixés sur une coque causent une perte de vitesse d'environ 15%. De plus, les organismes fixés détériorant la surface des coques, qu'elles soient constituées de bois, de métal ou de résine, la formulation vise ainsi à les protéger tout en diminuant leur fréquence de nettoyage .For example, a smooth shell thus treated with the formulation according to the invention offers less resistance to progress, such a treatment to reduce the hydrodynamic drag, increase speed and reduce fuel consumption. Indeed, 1 to 2 mm of algae and organisms attached to a hull cause a loss of speed of about 15%. In addition, the fixed organisms deteriorating the surface of the hulls, whether made of wood, metal or resin, the formulation aims to protect them while decreasing their frequency of cleaning.
A titre d'exemples, il est mentionné ci-dessous des formulations selon l'invention, sous forme de liquide ou de gel : Exemple 1 (aspect liquide) Résine copolymère styrène acryliqueAs examples, it is mentioned below formulations according to the invention, in the form of liquid or gel: Example 1 (liquid aspect) acrylic styrene copolymer resin
15,21% en poids d'extrait sec Eau 35,59% Co- solvant naphta en C8 à ClO15.21% by weight of dry extract Water 35.59% Co-solvent naphtha C8 to ClO
22,76% Co- solvant hydrocarbure aliphatique désaromatisé22.76% De-aromatized aliphatic hydrocarbon co-solvent
10,14%10.14%
Paraffine 7,08% en poids d'extrait sec Algicide 0,47%Paraffin 7.08% by weight of dry extract Algicide 0.47%
Talc 6,07%Talc 6.07%
Silice 0,71%Silica 0.71%
Tensioactif anioniqueAnionic surfactant
1,79% Epaississant 0,18%1.79% Thickener 0.18%
Exemple 2 (aspect liquide)Example 2 (liquid aspect)
Résine polyméthylsiloxane 40% en émulsion aqueuse non ionique40% polymethylsiloxane resin in aqueous nonionic emulsion
12,26% soit 4,9% en poids d'extrait sec Résine polyuréthane 35% en émulsion aqueuse12.26% or 4.9% by weight of dry extract 35% polyurethane resin in aqueous emulsion
18,62% soit 6,52% en poids d'extrait sec Résine copolymère styrène acrylique 40% en émulsion aqueuse18.62% or 6.52% by weight of dry extract 40% acrylic styrene copolymer resin in aqueous emulsion
5,03% soit 2,01% en poids d'extrait sec Eau 64,5% Paraffine 50% en émulsion aqueuse grade 56/585.03% or 2.01% by weight of dry extract Water 64.5% Paraffin 50% aqueous emulsion grade 56/58
39,88% soit 19,94% en poids d'extrait sec Huile essentielle (lavandin)39.88% or 19.94% by weight of dry extract essential oil (lavandin)
0,32%0.32%
Tensioactif à base de polymère d'acrylate de sodium 0,3%0.3% sodium acrylate polymer surfactant
Oxyde de silice 0,75% Epaississant polyuréthaneSilica oxide 0.75% Polyurethane thickener
0,34%0.34%
Epaississant acrylique 0,42% Exemple 3 (aspect liquide) :Acrylic thickener 0.42% Example 3 (liquid aspect):
Résine polyméthylsiloxane 40% en émulsion aqueuse non ionique40% polymethylsiloxane resin in aqueous nonionic emulsion
14,38% soit 5,75% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse 24,22% soit 12,11% en poids d'extrait sec14.38% or 5.75% by weight of solids content Polyurethane resin 50% in aqueous emulsion 24.22% or 12.11% by weight of solids
Eau 58,49%Water 58.49%
Paraffine 50% en émulsion aqueuse grade 56/58Paraffin 50% aqueous emulsion grade 56/58
37,66% soit 18,83% en poids d'extrait sec Co-solvant N-méthyl pyrrolydone 1,94%37.66% or 18.83% by weight of dry extract Co-solvent N-methyl pyrrolydone 1.94%
Tensioactif à base de polymère d'acrylate de sodiumSodium acrylate polymer surfactant
0,27%0.27%
Oxyde de silice 0,84% Epaississant polyuréthane 1,27%Silica oxide 0.84% Polyurethane thickener 1.27%
Epaississant acryliqueAcrylic thickener
0,51%0.51%
Exemple 4 (aspect gel) : Résine polyméthylsiloxane 40% en émulsion aqueuse non ioniqueExample 4 (gel appearance): 40% polymethylsiloxane resin in aqueous nonionic emulsion
10,94% soit 4,38% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse10.94% or 4.38% by weight of dry extract 50% polyurethane resin in aqueous emulsion
22,68% soit 11,34% en poids d'extrait sec Eau 56,39% Paraffine 50% en émulsion aqueuse grade 56/5822.68% or 11.34% by weight of dry extract Water 56.39% Paraffin 50% aqueous emulsion grade 56/58
41,89% soit 20,95% en poids d'extrait sec Co-solvant N-méthyl pyrrolydone41.89% or 20.95% by weight of dry extract Co-solvent N-methyl pyrrolydone
1,81%1.81%
Co-solvant éthanol 1,98% Tensioactif à base de polymère d'acrylate de sodiumCo-solvent ethanol 1.98% Sodium acrylate polymer surfactant
0,20%0.20%
Oxyde de silice 0,64% Epaississant acryliqueSilica oxide 0.64% acrylic thickener
2,32% Exemple 5 (aspect liquide) :2.32% Example 5 (liquid aspect):
Résine polyméthylsiloxane 40% en émulsion aqueuse non ionique40% polymethylsiloxane resin in aqueous nonionic emulsion
16,15% soit 6,46% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse 27,20% soit 13,60% en poids d'extrait sec16.15% or 6.46% by weight of solids content Polyurethane resin 50% in aqueous emulsion 27.20% or 13.60% by weight of solids
Eau 59,52%Water 59.52%
Paraffine 50% en émulsion aqueuse grade 56/58Paraffin 50% aqueous emulsion grade 56/58
30% soit 15% en poids d'extrait sec Co- solvant N-méthyl pyrrolydone 2,18%30% or 15% by weight of dry extract Co-solvent N-methyl pyrrolydone 2.18%
Tensioactif à base de polymère d'acrylate de sodiumSodium acrylate polymer surfactant
0,3%0.3%
Oxyde de silice 0,95% Epaississant polyuréthane 1,42%Silica oxide 0.95% Polyurethane thickener 1.42%
Epaississant acryliqueAcrylic thickener
0,57%0.57%
Exemple 6 (aspect liquide) : Résine polyméthylsiloxane 40% en émulsion aqueuse non ioniqueExample 6 (liquid aspect): 40% polymethylsiloxane resin in aqueous nonionic emulsion
18,45% soit 7,38% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse18.45% or 7.38% by weight of solids content Polyurethane resin 50% in aqueous emulsion
31,07% soit 15,54% en poids d'extrait sec Eau 60,88% Paraffine 50% en émulsion aqueuse grade 56/5831.07% or 15.54% by weight of dry extract Water 60.88% Paraffin 50% aqueous emulsion grade 56/58
20,02% soit 10,01% en poids d'extrait sec Co- solvant N-méthyl pyrrolydone20.02% or 10.01% by weight of dry extract Co-solvent N-methyl pyrrolydone
2,49%2.49%
Tensioactif à base de polymère d'acrylate de sodium 0,34%0.34% sodium acrylate polymer surfactant
Oxyde de silice 1,08% Epaississant polyuréthaneSilica oxide 1.08% Polyurethane thickener
1,63%1.63%
Epaississant acrylique 0,65% Exemple 7 (aspect liquide) :Acrylic Thickener 0.65% Example 7 (liquid aspect):
Résine polyméthylsiloxane 40% en émulsion aqueuse non ionique40% polymethylsiloxane resin in aqueous nonionic emulsion
16,17% soit 6,47% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse 27,24% soit 13,62% en poids d'extrait sec16.17%, ie 6.47% by weight of solids content Polyurethane resin 50% in aqueous emulsion 27.24%, ie 13.62% by weight of solids
Eau 54,71%Water 54.71%
Paraffine 50% en émulsion aqueuse grade 56/58Paraffin 50% aqueous emulsion grade 56/58
30,04% soit 15,02% en poids d'extrait sec Co-solvant ethanol d'origine végétal 4,91%30.04% is 15.02% by weight of dry extract Co-solvent ethanol of plant origin 4.91%
Co-so1vant N-méthy1 pyrrolydoneCo-solvent N-methyl pyrrolydone
2,18% Tensioactif à base de polymère d'acrylate de sodium2.18% Sodium acrylate polymer surfactant
0,30% Oxyde de silice 0,80% Epaississant polyuréthane0.30% Silica oxide 0.80% Polyurethane thickener
1,42% Epaississant acrylique1.42% Acrylic Thickener
0,57%0.57%
Exemple 8 (aspect liquide) :Example 8 (liquid aspect):
Résine polyméthylsiloxane 40% en émulsion aqueuse non ionique40% polymethylsiloxane resin in aqueous nonionic emulsion
14,38% soit 5,75% en poids d'extrait sec Résine polyuréthane 50% en émulsion aqueuse 24,22% soit 12,11% en poids d'extrait sec14.38% or 5.75% by weight of solids content Polyurethane resin 50% in aqueous emulsion 24.22% or 12.11% by weight of solids
Eau 54,12%Water 54.12%
Paraffine 50% en émulsion aqueuse grade 56/58Paraffin 50% aqueous emulsion grade 56/58
37,66% soit 18,83% en poids d'extrait sec Co-solvant ethanol d'origine végétal 4,36%37.66% or 18.83% by weight of dry extract Co-solvent ethanol of vegetable origin 4.36%
Co-solvant N-méthyl pyrrolydoneCo-solvent N-methyl pyrrolydone
1,94% Tensioactif à base de polymère d'acrylate de sodium1.94% Sodium acrylate polymer surfactant
0,27% Oxyde de silice 0,84% Epaississant polyuréthane0.27% Silica oxide 0.84% Polyurethane thickener
1,27% Epaississant acrylique1.27% Acrylic Thickener
0,51% Exemple 9 (aspect liquide) :0.51% Example 9 (liquid aspect):
Nappar 10 9%Nappar 10 9%
Ethanol 5%Ethanol 5%
Isopropanol 10% Mono propylène glycol 5%Isopropanol 10% Mono propylene glycol 5%
Octyphénol éthoxylé 2%Octyphenol ethoxylated 2%
Eau 30,99%Water 30.99%
Hydrofugeant Résine polyméthylsiloxane 14%Hydrofugant Resin polymethylsiloxane 14%
Epaississant 4% Paraffine 56/58 20%Thickener 4% Paraffin 56/58 20%
Biocide 0,01%Biocide 0.01%
Exemple 10 (aspect liquide) :Example 10 (liquid aspect):
Ester méthylique de colza 24% Mono propylène glycol 5%Rapeseed methyl ester 24% Mono propylene glycol 5%
Octyphénol éthoxylé 2%Octyphenol ethoxylated 2%
Eau 30,99%Water 30.99%
Hydrofugeant Résine polyméthylsiloxane 14%Hydrofugant Resin polymethylsiloxane 14%
Epaississant 4% Paraffine 56/58 20%Thickener 4% Paraffin 56/58 20%
Biocide 0,01%Biocide 0.01%
Exemple 11 (aspect liquide) :Example 11 (liquid aspect):
Linoléate de méthyle 15% Butanol primaire 3%Methyl linoleate 15% Primary butanol 3%
XyIène 6%XyIene 6%
Mono propylène glycol 5%Mono propylene glycol 5%
Octyphénol éthoxylé 2%Octyphenol ethoxylated 2%
Eau 30,99% Hydrofugeant Résine polyméthylsiloxane 14%Water 30,99% Hydrophobic Resin Polymethylsiloxane 14%
Epaississant 4%Thickener 4%
Paraffine 56/58 20%Paraffin 56/58 20%
Biocide 0,01% Exemple 12 (aspect liquide) :Biocide 0.01% Example 12 (liquid aspect):
Ester méthylique de colza 24%Rape methyl ester 24%
Mono propylène glycol 5%Mono propylene glycol 5%
Octyphënol éthoxylé 2% Eau 30,99%Ethoxylated Octyphenol 2% Water 30.99%
Hydrofugeant Résine polyméthylsiloxane 19%Water repellent Polymethylsiloxane resin 19%
Epaississant 4%Thickener 4%
Paraffine 56/58 15%Paraffin 56/58 15%
Biocide 0,01%Biocide 0.01%
Exemple 13 (aspect liquide) :Example 13 (liquid aspect):
Méthoxy propanol 24%Methoxy propanol 24%
Mono propylène glycol 5%Mono propylene glycol 5%
Octyphénol éthoxylé 2% Eau ' 30,99%Octylphenol ethoxylate 2% Water '30.99%
Hydrofugeant Résine polyméthylsiloxane 19%Water repellent Polymethylsiloxane resin 19%
Epaississant 4%Thickener 4%
Paraffine 56/58 15%Paraffin 56/58 15%
Biocide 0,01%Biocide 0.01%
Exemple 14 (aspect liquide) :Example 14 (liquid aspect):
XyIène 20%XyIene 20%
Mono propylène glycol 5%Mono propylene glycol 5%
Octyphénol éthoxylé 2% Eau 30,99%Ethoxylated Octyphenol 2% Water 30.99%
Résine polysiloxane 23%Polysiloxane resin 23%
Epaississant 4%Thickener 4%
Paraffine 56/58 15%Paraffin 56/58 15%
Biocide 0,01%Biocide 0.01%
Les exemples de formulations ci-dessus peuvent avantageusement comprendre environ 0,2% d'un colorant tel qu'un pigment inorganique, par exemple l'iron chromium hématite (marron) , le cobalt chromite green spinel (vert) , le cobalt aluminate spinel (bleu) , le copper chrome black spinelThe examples of above formulations may advantageously comprise about 0.2% of a dye such as an inorganic pigment, for example iron chromium hematite (brown), cobalt chromite green spinel (green), cobalt aluminate spinel (blue), the copper chrome black spinel
(noir) , le dioxyde de titane (blanc) . De plus, l'invention est illustrée, par le test d'efficacité ci-après, réalisé dans le port Camille Rayon de Golfe-Juan (Alpes-Maritimes) , port en eau peu profonde, très fermé, sans circulation d'eau, et très chargé en vase. Ce test vise à mettre en évidence l'efficacité de la formulation selon l'invention comme agent antisalissure destiné à défavoriser l'accroche des organismes marins tels que les algues, coquillages et autres crustacés sur tout support immergé . Le test est réalisé avec des plaquettes de petite dimension (30 cm * 20 cm) , en contreplaqué marin, initialement revêtues recto/verso d'une couche primaire époxy de couleur blanche, immergées à une profondeur d'environ 1,50 m.(black), titanium dioxide (white). In addition, the invention is illustrated by the efficiency test below, carried out in the Port Camille Rayon of Golfe-Juan (Alpes-Maritimes), port in shallow water, very closed, without circulation of water, and very loaded in vase. This test aims to highlight the effectiveness of the formulation according to the invention as anti-fouling agent intended to disadvantage the adhesion of marine organisms such as algae, shells and other crustaceans on any submerged support. The test is carried out with small plates (30 cm * 20 cm), made of marine plywood, initially coated on both sides with a white epoxy primer layer, immersed to a depth of approximately 1.50 m.
Deux formulations sont ainsi comparativement testées, après application de trois couches successives au pinceau : la plaquette A est revêtue de la formulation selon l'invention telle que définie ci-dessus dans l'exemple 9, aqueuse, hydrophobe et super oléophobe, transparente ; et la plaquette B est revêtue d'une peinture antisalissure à base de sels de cuivre, substances désormais interdites par la norme Européenne REACH, de chez INTERNATIONAL groupe AKZO NOBEL, référence CRUISER UNO de couleur bleue.Two formulations are thus comparatively tested, after application of three successive layers with the brush: the wafer A is coated with the formulation according to the invention as defined above in Example 9, aqueous, hydrophobic and super oleophobic, transparent; and the plate B is coated with an antifouling paint based on copper salts, substances now banned by the European REACH standard, from INTERNATIONAL group AKZO NOBEL, reference CRUISER UNO blue.
Les plaquettes ont été photographiées lors de leur mise à l'eau le 01/10/2008 telles qu'illustrées dans les figures IA et IB, puis lors de leur sortie le 03/12/2008 telles qu'illustrées dans les figures 2A et 2B .The chips were photographed during their launch on 01/10/2008 as illustrated in Figures IA and IB, then on their release on 03/12/2008 as illustrated in Figures 2A and 2B.
A cet effet, les figures IA et IB mettent en évidence l'aspect de la plaquette A et de la plaquette B avant leur mise à l'eau. Les deux plaquettes A et B apparaissent complètement propres, dépourvues de toute quelconque salissure et autre dépôt marin.For this purpose, Figures IA and IB highlight the appearance of the wafer A and the plate B before their launch. Both pads A and B appear completely clean, free of any dirt and other marine deposits.
Les figures 2A et 2B montrent respectivement l'aspect de ces mêmes plaquettes A et B, après 64 jours d'immersion dans de l ' eau de mer . D'après les résultats obtenus, la plaquette A, sur laquelle on a appliqué trois couches de la formulation selon l'invention, est revêtue d'un léger dépôt de vase et ne comporte aucune colonisation par des balanes ou des bernacles.FIGS. 2A and 2B respectively show the appearance of these same plates A and B after 64 days of immersion in seawater. According to the results obtained, the plate A, on which three layers of the formulation were applied according to the invention is covered with a slight vase deposit and does not involve any colonization by barnacles or barnacles.
De même, la plaquette B, est recouverte d'un dépôt de vase similaire à celui obtenu sur la plaquette A, et ne comporte aucune colonisation par des balanes ou des bernacles.In the same way, the plate B, is covered with a vase deposit similar to that obtained on the plate A, and does not involve any colonization by barnacles or barnacles.
La plaquette A, traitée avec la formulation selon l'invention, suivant les résultats obtenus à partir du test réalisé, défavorise ainsi l'accroche des organismes marins tels que les algues, coquillages et autres crustacés, et limite le dépôt par exemple de vase. La formulation selon l'invention offre ainsi une nouvelle alternative de revêtement antisalissure ayant une efficacité comparable à une peinture antisalissure à base de biocide tout en améliorant le respect à l'environnement et à la santé humaine. Bien entendu, l'invention ne se limite pas aux modes de réalisation et aux exemples présentés ci-dessus et l'homme du métier, grâce à des opérations de routine, pourra être amené à réaliser d'autres modes de réalisation non décrits explicitement, qui entrent dans le cadre large de l'invention. The wafer A, treated with the formulation according to the invention, according to the results obtained from the test carried out, thus disadvantages the grip of marine organisms such as algae, shells and other crustaceans, and limits the deposit for example of silt. The formulation according to the invention thus offers a new alternative anti-fouling coating having an efficiency comparable to a biocide-based antifouling paint while improving respect for the environment and human health. Of course, the invention is not limited to the embodiments and to the examples presented above, and the person skilled in the art, by virtue of routine operations, may be led to make other embodiments that are not explicitly described. which fall within the broad scope of the invention.

Claims

REVENDICATIONS
1. Formulation d'un système de revêtement antisalissure destinée à être appliquée à des supports immergés, caractérisée en ce qu'elle comprend au moins 30% en poids du poids total d'eau, au moins 10% en poids d'extrait sec du poids total d'un hydrofugeant choisi parmi une résine silicone, une résine polyuréthane et/ou une résine copolymère styrène acrylique, prise seule ou en mélange et au moins 5% en poids d'extrait sec du poids total d'un agent actif antiadhérent .1. Formulation of an anti-fouling coating system intended to be applied to submerged supports, characterized in that it comprises at least 30% by weight of the total weight of water, at least 10% by weight of dry extract of total weight of a water repellent chosen from a silicone resin, a polyurethane resin and / or a styrene acrylic copolymer resin, taken alone or as a mixture and at least 5% by weight of dry extract of the total weight of an antiadhesive active agent.
2. Formulation selon la revendication 1, caractérisée en que l ' hydrofugeant à base de résine silicone est une résine siloxane, polysiloxane, et/ou leurs dérivés, prise seule ou en mélange .2. Formulation according to claim 1, characterized in that the waterproofing agent based on silicone resin is a siloxane resin, polysiloxane, and / or their derivatives, taken alone or in admixture.
3. Formulation selon la revendication 2, caractérisée en ce que l ' hydrofugeant à base de résine silicone est une résine polyméthylsiloxane en êmulsion aqueuse non ionique.3. Formulation according to claim 2, characterized in that the waterproofing agent based on silicone resin is a polymethylsiloxane resin in nonionic aqueous emulsion.
4. Formulation selon l'une des revendications précédentes, caractérisée en ce que l'agent actif anti-adhérent est une cire, une graisse ou de la paraffine.4. Formulation according to one of the preceding claims, characterized in that the anti-adherent active agent is a wax, a fat or paraffin.
5. Formulation selon l'une des revendications précédentes, caractérisé en ce qu'elle comprend au moins 50% en poids du poids total d'un système solvant - co- solvant aqueux.5. Formulation according to one of the preceding claims, characterized in that it comprises at least 50% by weight of the total weight of an aqueous solvent-co-solvent system.
6. Formulation selon la revendication 5, caractérisée en ce qu'elle comprend au moins 20% en poids du poids total d'un co-solvant choisi parmi les hydrocarbures, alcools, cétones, esters, pris seul ou en combinaison.6. Formulation according to claim 5, characterized in that it comprises at least 20% by weight of the total weight of a co-solvent selected from hydrocarbons, alcohols, ketones, esters, taken alone or in combination.
7. Formulation selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend en outre un agent non toxique, naturel, apte à repousser l'accroche en particulier des algues, composé de souches bactériennes à une concentration inférieure à 5% en poids du poids total.7. Formulation according to one of the preceding claims, characterized in that it further comprises a non-toxic agent, natural, able to repel the grip particularly algae, consisting of bacterial strains at a concentration of less than 5% by weight of the total weight.
8. Formulation selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend :8. Formulation according to one of the preceding claims, characterized in that it comprises:
Résine copolymère styrène acryliqueAcrylic styrene copolymer resin
15,21% en poids d'extrait sec15.21% by weight of dry extract
Eau 35,59%Water 35.59%
Co- solvant naphta en C8 à ClO 22,76%Co-solvent naphtha C8 to ClO 22.76%
Co-solvant hydrocarbure aliphatique désaromatiséDe-aromatized aliphatic hydrocarbon co-solvent
10,14%10.14%
Paraffine 7,08% en poids d'extrait secParaffin 7.08% by weight of dry extract
Algicide 0,47% Talc 6,07%Algicide 0.47% Talc 6.07%
Silice 0,71%Silica 0.71%
Tensioactif anioniqueAnionic surfactant
1,79%1.79%
Epaississant 0,18%Thickener 0.18%
9. Procédé de traitement de supports destinés à être immergés avec une formulation selon l'une des revendications 1 à 8, caractérisé en ce que la formulation est appliquée en au moins une couche par pulvérisation, au rouleau ou au pinceau sur le support à protéger contre les salissures marines, après nettoyage et séchage préalable du support, à une température extérieure comprise entre environ 5° et environ 500C, préfèrentiellement entre environ 15° et environ 300C, puis est séchée à température ambiante, par exemple 230C, pendant environ 25 minutes et environ 40 minutes entre deux couches successives, et entre environ 30 minutes et environ 50 minutes avant la mise à l'eau.9. Process for treating supports intended to be immersed with a formulation according to one of claims 1 to 8, characterized in that the formulation is applied in at least one layer by spraying, roller or brush on the support to be protected. against marine fouling after cleaning and pre-drying of the support, at an external temperature between about 5 ° and about 50 0 C., preferably between about 15 ° and about 30 0 C and then dried at room temperature, for example 23 0 C, for about 25 minutes and about 40 minutes between two successive layers, and between about 30 minutes and about 50 minutes before launching.
10. Utilisation d'une formulation selon l'une des revendications l à 8, comme agent antisalissure destiné à défavoriser l'accroche des organismes marins tels que les algues, coquillages et autres crustacés sur tout support immergé et notamment les carènes des navires . 10. Use of a formulation according to one of claims 1 to 8, as anti-fouling agent intended to disadvantage the adhesion of marine organisms such as algae, shells and other crustaceans on any submerged support including the hulls of ships.
EP10713479A 2009-03-13 2010-03-15 Aqueous formulation for an antifouling coating system for submerged substrates, method for treating same, and use thereof Withdrawn EP2406329A1 (en)

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FR0901175A FR2943066B1 (en) 2009-03-13 2009-03-13 AQUEOUS FORMULATION OF AN ANTI-SLIP COATING SYSTEM FOR SUBMERSIBLE SUBSTRATES, PROCESSING METHOD AND USE THEREOF
FR0903562A FR2943067B1 (en) 2009-03-13 2009-07-20 AQUEOUS FORMULATION OF AN ANTI-SLIP COATING SYSTEM FOR SUBMERSIBLE SUBSTRATES, PROCESSING METHOD AND USE THEREOF
PCT/FR2010/000213 WO2010103209A1 (en) 2009-03-13 2010-03-15 Aqueous formulation for an antifouling coating system for submerged substrates, method for treating same, and use thereof

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