EP2406329A1

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

Info

Publication number: EP2406329A1
Application number: EP10713479A
Authority: EP
Inventors: Véronique ROULLEAUX; Patrick Frangoulis
Original assignee: Seawax Marine Coatings
Current assignee: Seawax Marine Coatings
Priority date: 2009-03-13
Filing date: 2010-03-15
Publication date: 2012-01-18
Also published as: FR2943067A1; US8545615B2; WO2010103209A1; FR2943066B1; US20120004357A1; FR2943067B1; BRPI1009104A2; FR2943066A1

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

AQUEOUS FORMULATION OF AN ANTI-SLIP COATING SYSTEM FOR SUBMERSIBLE SUBSTRATES, PROCESSING METHOD AND SAME

USE

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.

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.

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.

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.

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.

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.

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.

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).

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.

Such biocide-based anti-fouling paints thus contain one or more toxic molecules and prove to be polluting.

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.

Other 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 ^®) of 2, 4, 5, 6-tetrachloroisophthalonitrile

(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.

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.

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.

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.

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.

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.

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.

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:

- 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 formulation dries rapidly at room temperature; and

- 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.

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.

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.

The formulation 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.

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.

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.

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.

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.

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.

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.

As a nonlimiting example of ketones according to the invention, N-methyl pyrrolidone may be mentioned preferentially.

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.

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.

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.

By way of non-limiting example of a 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.

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.

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.

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. 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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%.

It is difficult to obtain a single-phase homogeneous mixture in the presence of a large quantity, for example at least

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.

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%.

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.

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.

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:

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;

- 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.

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:

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;

the compounds obtained in the following order are then added to the liquid phase obtained: a first part of

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;

- Finally, we add the water so as to obtain a homogeneous phase to a single phase, stable over time.

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.

The techniques and mixing times are known to those skilled in the art and are adapted to the quantities used.

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.

In use, 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.

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.

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. 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.

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.

For optimal application of the formulation according to the invention, 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.

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.

Advantageously, 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.

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.

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.

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.

As 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% by weight of dry extract Water 35.59% Co-solvent naphtha C8 to ClO

22.76% De-aromatized aliphatic hydrocarbon co-solvent

10.14%

Paraffin 7.08% by weight of dry extract Algicide 0.47%

Talc 6.07%

Silica 0.71%

Anionic surfactant

1.79% Thickener 0.18%

Example 2 (liquid aspect)

40% polymethylsiloxane resin in aqueous nonionic emulsion

12.26% or 4.9% by weight of dry extract 35% polyurethane resin in aqueous emulsion

18.62% or 6.52% by weight of dry extract 40% acrylic styrene copolymer resin in aqueous emulsion

5.03% or 2.01% by weight of dry extract Water 64.5% Paraffin 50% aqueous emulsion grade 56/58

39.88% or 19.94% by weight of dry extract essential oil (lavandin)

0.32%

0.3% sodium acrylate polymer surfactant

Silica oxide 0.75% Polyurethane thickener

0.34%

Acrylic thickener 0.42% Example 3 (liquid aspect):

40% polymethylsiloxane resin in aqueous nonionic emulsion

14.38% or 5.75% by weight of solids content Polyurethane resin 50% in aqueous emulsion 24.22% or 12.11% by weight of solids

Water 58.49%

Paraffin 50% aqueous emulsion grade 56/58

37.66% or 18.83% by weight of dry extract Co-solvent N-methyl pyrrolydone 1.94%

Sodium acrylate polymer surfactant

0.27%

Silica oxide 0.84% Polyurethane thickener 1.27%

Acrylic thickener

0.51%

Example 4 (gel appearance): 40% polymethylsiloxane resin in aqueous nonionic emulsion

10.94% or 4.38% by weight of dry extract 50% polyurethane resin in aqueous emulsion

22.68% or 11.34% by weight of dry extract Water 56.39% Paraffin 50% aqueous emulsion grade 56/58

41.89% or 20.95% by weight of dry extract Co-solvent N-methyl pyrrolydone

1.81%

Co-solvent ethanol 1.98% Sodium acrylate polymer surfactant

0.20%

Silica oxide 0.64% acrylic thickener

2.32% Example 5 (liquid aspect):

40% polymethylsiloxane resin in aqueous nonionic emulsion

16.15% or 6.46% by weight of solids content Polyurethane resin 50% in aqueous emulsion 27.20% or 13.60% by weight of solids

Water 59.52%

Paraffin 50% aqueous emulsion grade 56/58

30% or 15% by weight of dry extract Co-solvent N-methyl pyrrolydone 2.18%

Sodium acrylate polymer surfactant

0.3%

Silica oxide 0.95% Polyurethane thickener 1.42%

Acrylic thickener

0.57%

Example 6 (liquid aspect): 40% polymethylsiloxane resin in aqueous nonionic emulsion

18.45% or 7.38% by weight of solids content Polyurethane resin 50% in aqueous emulsion

31.07% or 15.54% by weight of dry extract Water 60.88% Paraffin 50% aqueous emulsion grade 56/58

20.02% or 10.01% by weight of dry extract Co-solvent N-methyl pyrrolydone

2.49%

0.34% sodium acrylate polymer surfactant

Silica oxide 1.08% Polyurethane thickener

1.63%

Acrylic Thickener 0.65% Example 7 (liquid aspect):

40% polymethylsiloxane resin in aqueous nonionic emulsion

16.17%, ie 6.47% by weight of solids content Polyurethane resin 50% in aqueous emulsion 27.24%, ie 13.62% by weight of solids

Water 54.71%

Paraffin 50% aqueous emulsion grade 56/58

30.04% is 15.02% by weight of dry extract Co-solvent ethanol of plant origin 4.91%

Co-solvent N-methyl pyrrolydone

2.18% Sodium acrylate polymer surfactant

0.30% Silica oxide 0.80% Polyurethane thickener

1.42% Acrylic Thickener

0.57%

Example 8 (liquid aspect):

40% polymethylsiloxane resin in aqueous nonionic emulsion

Water 54.12%

Paraffin 50% aqueous emulsion grade 56/58

37.66% or 18.83% by weight of dry extract Co-solvent ethanol of vegetable origin 4.36%

Co-solvent N-methyl pyrrolydone

1.94% Sodium acrylate polymer surfactant

0.27% Silica oxide 0.84% Polyurethane thickener

1.27% Acrylic Thickener

0.51% Example 9 (liquid aspect):

Nappar 10 9%

Ethanol 5%

Isopropanol 10% Mono propylene glycol 5%

Octyphenol ethoxylated 2%

Water 30.99%

Hydrofugant Resin polymethylsiloxane 14%

Thickener 4% Paraffin 56/58 20%

Biocide 0.01%

Example 10 (liquid aspect):

Rapeseed methyl ester 24% Mono propylene glycol 5%

Octyphenol ethoxylated 2%

Water 30.99%

Hydrofugant Resin polymethylsiloxane 14%

Thickener 4% Paraffin 56/58 20%

Biocide 0.01%

Example 11 (liquid aspect):

Methyl linoleate 15% Primary butanol 3%

XyIene 6%

Mono propylene glycol 5%

Octyphenol ethoxylated 2%

Water 30,99% Hydrophobic Resin Polymethylsiloxane 14%

Thickener 4%

Paraffin 56/58 20%

Biocide 0.01% Example 12 (liquid aspect):

Rape methyl ester 24%

Mono propylene glycol 5%

Ethoxylated Octyphenol 2% Water 30.99%

Water repellent Polymethylsiloxane resin 19%

Thickener 4%

Paraffin 56/58 15%

Biocide 0.01%

Example 13 (liquid aspect):

Methoxy propanol 24%

Mono propylene glycol 5%

Octylphenol ethoxylate 2% Water ^'30.99%

Water repellent Polymethylsiloxane resin 19%

Thickener 4%

Paraffin 56/58 15%

Biocide 0.01%

Example 14 (liquid aspect):

XyIene 20%

Mono propylene glycol 5%

Ethoxylated Octyphenol 2% Water 30.99%

Polysiloxane resin 23%

Thickener 4%

Paraffin 56/58 15%

Biocide 0.01%

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

(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.

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.

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.

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.

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.

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.

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

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 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 according to claim 2, characterized in that the waterproofing agent based on silicone resin is a polymethylsiloxane resin in nonionic aqueous emulsion.

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 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 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 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 according to one of the preceding claims, characterized in that it comprises:

Acrylic styrene copolymer resin

15.21% by weight of dry extract

Water 35.59%

Co-solvent naphtha C8 to ClO 22.76%

De-aromatized aliphatic hydrocarbon co-solvent

10.14%

Paraffin 7.08% by weight of dry extract

Algicide 0.47% Talc 6.07%

Silica 0.71%

Anionic surfactant

1.79%

Thickener 0.18%

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. 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.