Antifouling compositions comprising a polymer with salt groups

[0001] The present invention relates to anti-fouling paint, in particular for marine fleet applications.

[0002] Man-made structures such as ship hulls, buoys, oil rigs, oil drilling rigs, and pipes located under the water surface are susceptible to contamination by aquatic organisms such as algae green algae, brown algae, barnacles, mussels and the like. These types of structures are usually made of metal, but may also contain other structural materials such as concrete. Such contaminants are burdensome for ship hulls because they increase frictional resistance when moving in water, consequently reducing speed and increasing fuel cost. Pollution is a nuisance on static structures such as the pillars of oil rigs or drilling rigs for oil extraction, firstly the resistance of thick layers of pollution that they pose to waves and currents can cause unpredictable and potentially dangerous stresses in the structure, and secondly impurities inspect the structure for defects such like stress cracks and corrosion. Contaminants are a nuisance on pipes such as cooling water inlets and outlets because they reduce the effective cross-section of the pipe and consequently the flow rate is reduced.

[0003] It is known to use anti-fouling paints, for example as a top layer on ship hulls, to slow down the subsidence and growth of marine organisms such as barnacles and algae by releasing biocides acting on marine organisms.

[0004] Traditionally, antifouling paints consist of an inert binder with a biocidal pigment that is leached from the paint. The binders used were vinyl resins and rosin. Vinyl resins are insoluble in sea water and paints based on them require the use of high concentrations of pigment so as to get contact between the pigment particles and ensure leaching. Rosin is a hard and brittle resin that is very slightly soluble in sea water. Rosin-based antifouling paints are referred to as soluble or eroding paints. The biocidal pigment is gradually washed away from the matrix containing the rosin binder, leaving the rosin matrix skeleton which is washed off the hull surface allowing the biocidal pigment to be washed from the deeper layers of paint.

[0005] In recent years, many successful paints have been "self-polishing copolymer" paints based on a polymeric binder with which biocidal organotric triin groups were chemically bonded and from which said biocidal groups are gradually hydrolyzed by sea water. In such systems, the side groups in the linear polymer unit are disconnected in the first stage of reaction with sea water, as a result of which the polymer matrix which remains, becomes water-soluble or disperses in it. In the second stage, the water-soluble or water-dispersible polymer matrix in the top coat of paint on the ship is washed away or eroded. Paints of this type are described, for example, in GB-A1 457 590.

[0006] Since the use of organotin compounds has been banned worldwide, there is a need to find alternative antifouling substances that could be used in antifouling compositions. Paints with self-polishing copolymers that release non-biocidal

EP 1 753 829 chemical groups, described in patents EP-A-69 559, EP-A-204 456, EP-A-529 693, EP-A779 304, WO-A-91/14743, WO-A-91 / 09915, GB-A-231 070, and JP-A-9-286933.

[0007] US-A-4,675,051 describes an anti-fouling paint for ships which gradually dissolves in sea water and which consists of a binder in the form of a resin obtained by reaction of rosin with an aliphatic polyamine containing at least one primary or secondary amino group. EP-A-802 243 describes a coating composition consisting of rosin, a polymer containing organosilyl ester groups and an anti-fouling substance.

[0008] WO-A-02/02698 describes an antifouling paint that gradually dissolves in sea water. The paint contains a binder and an ingredient with biocide properties. The binder contains rosin material and an auxiliary film-forming resin. The auxiliary film-forming resin contains a non-hydrolyzing, water-insoluble film-forming polymer and a polymer containing acidic functional groups, also film-forming, wherein the acidic groups are protected by quaternary ammonium groups or quaternary phosphonium groups. In the first stage, the protecting groups are hydrolysed, dissociated or exchanged with the species found in seawater, and as a result the remaining polymer matrix becomes soluble or dispersed in seawater. In the second stage, the soluble or dispersible polymer matrix in the top coat of paint on the ship is washed away or eroded.

[0009] The structure of quaternary ammonium groups or quaternary phosphonium groups, used as protecting groups in polymers containing acid functional groups, affects the rate at which paint dissolves or erodes. Although long-chain quaternary ammonium groups provide longer paint degradation, they are more toxic with increasing size. Such toxicity is used, for example, in mold protection coating compositions described in JP-A-2-120372.

[0010] GB-A-2 273 934 describes an adhesive system that is alternative to antifouling systems based on organotin compounds. One of the hydrolysable polymer binders described contains haloamino salt groups associated with the polymer backbone. Such a polymeric binder is prepared by copolymerizing monomers of halogenamine salts that contain a (meth) acrylamide functional group. Such polymer binders are partially soluble in sea water due to the presence of salt-halogenoamino groups. Nevertheless, as the binder is somewhat soluble in sea water from the very beginning, the paint erodes relatively quickly.

[0011] JP-A-07 082511 describes another binder system that is an alternative to antifouling systems based on organotin compounds. One of the hydrolysable polymer binders described contains phosphonium salt groups associated with the polymer backbone. The counterion for the phosphonium group is a small group, for example a halide ion, formic acid, acetic acid or oxalic acid residue, sulfate ion, or ion derived from phosphoric acid. This type of polymer binders are partly soluble in sea water which is associated with the presence of functional groups of the phosphonium salt. Nevertheless, as the binder is somewhat soluble in sea water from the very beginning, the paint erodes relatively quickly.

EP 1 753 829 [0012] The above-described salt-containing binders are an alternative to tin-based systems, however their erosion rate is relatively high. Consequently, there is a need to find a polymeric binder containing salt groups that from the beginning is relatively poorly soluble in seawater, and at the same time such that the counterions are hydrolysed, detached or exchanged with the species present in seawater, and as a result that the remaining polymer matrix becomes soluble or dispersed in sea water.

[0013] The present invention relates to a polymer-containing antifouling coating composition that provides a solution to the above-mentioned problems / disadvantages in antifouling compositions, and to the use of antifouling compositions for protecting man-made submerged structures such as ship hulls, buoys, drilling platforms, drilling rigs for oil extraction and pipes.

[0014] The present invention provides antifouling coating compositions according to claim 1 and their uses according to claim 9.

[0015] The polymer binder used in the present invention is a polymer containing one or more functional group in the form of an ammonium salt or one or more functional group in the form of a phosphonium salt which are associated (as a side group) with the polymer backbone, said salts contain, as a counterion, an anionic acid residue having an aliphatic, aromatic, or alkylaryl hydrocarbon group consisting of at least 5, preferably at least 6 carbon atoms.

[0016] The polymer comprises a salt of the primary and / or secondary and / or tertiary amine and / or a salt of the primary and / or secondary and / or tertiary phosphine. These types of polymers are described, for example, in JP 63-273609. A Japanese document describes the use of this type of polymers as coagulating agents in wastewater containing large amounts of organic material.

[0017] The polymer containing salt groups used in the present invention is obtained by a process comprising the following steps:

- Reaction of the long chain acid with an amino- or phosphine-substituted monomer of formula (II):

<img file="PL1753829T3_D0001.tif" />

Where Y is O or NH, Z is N or P, R¹ is a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen or a C1-C2 alkyl group. R² is a C2-C12 disubstituted hydrocarbon group, preferably a C2-C8 disubstituted hydrocarbon group, more preferably a C2-C4 disubstituted hydrocarbon group.

R³ and R⁴ independently represent a hydrogen atom or a C1-C8 alkyl group, preferably methyl, or an optionally substituted phenyl group.

EP 1 753 829

The above reaction leads to a monomer containing an amino functional salt and / or a phosphine functional salt, said salt, as a counterion, contains an anionic residue of an acid having an aliphatic, aromatic or alikylaryl hydrocarbon group consisting of at least 5, preferably at least 6 carbon atoms ( see formula (I) above). Quaternary ammonium groups and quaternary phosphonium groups are not formed in this reaction.

- Polymerization of at least one type of monomer containing salt groups, which monomer contains an amino salt group and / or a phosphine salt group.

[0018] The acid having an aliphatic, aromatic or alikylaryl hydrocarbon group consisting of 5 or more, preferably 6 or more carbon atoms is used as the long chain acid in the first-mentioned step. For example, the acid may be carbonic acid, sulfonic acid, or sulfuric acid. Preferably the acid contains 5 or more, more preferably 6 or more carbon atoms, and even more preferably 8 or more carbon atoms. The acid may be branched. Acids may contain cyclic groups. Suitable acids are, for example, palmitic acid, stearic acid, ethylhexanoic acid, rosin, and rosin derivatives containing acid functional groups. The acid preferably contains up to 50 carbon atoms, more preferably up to 30 carbon atoms, even more preferably up to 20 carbon atoms, and most preferably up to 16 carbon atoms. Optionally, the acid is a compound having acidic functional groups with biocide properties, such as (9E) -4- (6,10-dimethylocta9.11-dienyl) furan-2-carboxylic acid or p- (sulfooxy) cinnamic acid (zwitteric acid) .

[0019] The polymerization of a salt-containing monomer or a mixture of salt-containing monomers is carried out using a variety of comonomers, optionally mixtures of comonomers. For example, the addition copolymerization is carried out with an unsaturated monomer prepared by reacting an alkyl, alkoxyalkyl, carboxylic or heterocyclic alcohol or amine ester or amine with an unsaturated carboxylic acid, an example is methyl or methacrylate acrylate, butyl acrylate, isobutyl acrylate or methacrylate or methacrylate. Alternatively, the unsaturated comonomer is a vinyl compound, for example styrene, vinylpyrrolidone or vinyl acetate.

[0020] The polymerization of the salt-containing monomer is carried out using long-chain, acid-protected monomers with quaternary ammonionic groups and / or using long-chain, acid-protected monomers with quaternary phosphonium groups. These types of monomers and their polymerization are described in WO2004 / 018533. The quaternary ammonium functional group and the quaternary phosphonium functional group of such monomer is "long chain, acid protected", ie it is neutralized by a counterion which contains an anionic acid residue having an aliphatic, aromatic or alkylaryl hydrocarbon group consisting of 6 or more carbon atoms. Thus, the resulting polymer contains a salt of a primary and / or secondary and / or tertiary amine and / or a salt of the primary and / or secondary and / or tertiary phosphine, and it is functionalized with a quaternary ammonium group and / or a quaternary phosphonium group. Such a system is called a mixed system.

[0021] The polymerization of salt-containing monomers is preferably carried out using at least 5 mol% of salt-containing monomer, more preferably at least 10 mol%. The polymerization is preferably carried out using less than 40 mol% of the monomer containing salt groups, more preferably less than 30 mol%. In the case where the polymerization is carried out using monomers containing salt groups as well as quaternary functionalized monomers, the total amount of monomers containing salt groups plus quaternary functionalized monomers is preferably at least 5 mol%, more preferably 10 mol%, and preferably less than 40 mol%, more preferably less than 30 mol%.

[0022] Preferably, a polymer having one or more amine salt function and / or one or more phosphine salt function, attached (as a side group) to the polymer backbone, which is at least 5 mol% is used. from a monomer containing salt groups based on the total number of monomers from which the polymer is composed. More preferably the polymer consists of at least 10 mol% of a monomer containing salt groups. Preferably a polymer is used which contains no more than 40 mol% of the monomer with salt groups, more preferably no more than 30 mol%.

[0023] It is also preferred to use a polymer comprising one or more monomer with salt groups and one or more quaternary functional monomer, wherein the total amount of salt monomers plus the quaternary functional monomers is at least 5 mol%, more preferably at least 10 mol%, preferably less than 40 mol%, more preferably less than 30 mol%.

[0024] It is also preferred to use a mixture of polymers containing one or more amine functional salt character and / or one or more phosphine functional salt group and optionally polymers containing one or more quaternary ammonium and / or quaternary phosphonium functional group (as groups side) with polymer main chains. These mixtures contain at least 5 mol% of monomers containing salt groups plus (optionally present) quaternary functional monomers calculated on the total amount of monomers from which the polymers forming the mixture are made. More preferably the mixture contains at least 10 mol% of salt-containing monomers plus quaternary functional monomers. Preferably, a polymer mixture is used which contains no more than 40 mol% of monomers containing salt groups plus quaternary functional monomers, more preferably no more than 30 mol%.

[0025] Preferably, the coating composition comprises a polymer with one or more amine functional salt group and / or one or more phosphine functional salt group bonded (as a side group) to the polymer backbone, which contains at least 5 mol% of monomers with groups salt-like, more preferably at least 10 mol%. Preferably, the coating composition comprises a polymer with less than 40 mol% monomer content with salt groups, more preferably with less than 30 mol%.

[0026] Also preferred is a coating composition that comprises a polymer with one or more monomers having groups of salts and one or more monomers with quaternary groups

% Of total monomers with salt groups plus monomers with quaternary groups is at least 5 mol%, more preferably at least 10 mol%, and preferably less than 40 mol%, more preferably less than 30 mol%.

[0027] Also preferred is a coating composition comprising a mixture of polymers with one or more amino functional salts and / or one or more phosphine functional salts and optionally polymers with one or more quaternary ammonium and / or one or more quaternary a phosphonium group attached (as a side group) to the polymer backbone, wherein said mixture contains at least 5 mol% salt monomers plus (optionally present) quaternary monomers, more preferably at least 10 mol%.

[0028] Preferably, the coating composition comprises a polymer blend with not more than 40 mol% salt content monomers plus quaternary functional monomers, more preferably not more than 30 mol%.

[0029] In a preferred embodiment of the invention, the counter ions in the salt group in polymers containing one or more salt amino group and / or one or more salt phosphine group usually have low toxicity or are not even biocides. In this case, the antifouling coating composition of the present invention should comprise a separate component with biocidal properties relative to marine organisms.

[0030] In a further preferred embodiment of the invention, the salts in the polymer containing one or more amino functional salts and / or one or more phosphine functional salts contain, as counterion, a biocidal component with respect to marine organisms. In such a case, the antifouling coating composition of the present invention comprises a separate biocidal component present as a co-biocide. The advantage of incorporating the biocide into salt groups in the polymer is that the release rate of the embedded biocide depends on the ion exchange rate, which is better controlled than the release rate depending on the diffusion rate. The acid function biocide used as counterion can be a natural or synthesized compound and can be obtained from natural products. For example, an acid function biocide used as a counter ion may be material obtained from marine organisms. Preferably, the biocide is rapidly degraded in a marine environment.

[0031] The polymer matrix, i.e. the binder that dissolves in or disperses in seawater (after or during hydrolysis, separation or exchange of counterions with individuals in seawater) preferably has low toxicity, most preferably it is not a biocide.

[0032] The rate at which the cured coating prepared with antiperspirant coating composition according to the present invention dissolves or erodes in seawater is controlled by the selection of the structure of the long chain acid residues being counter ions without serious problems associated with the toxicity of the released groups. Long chain acid residues that are counterions contain, for example, long chains and / or branched chains and / or cyclic groups. By changing the hydrophobicity of long-chain acid residues that are counter-ions, the rate at which the coating dissolves or erodes in seawater is regulated. Also the selection of the right amounts of monomers with salt groups was used to prepare the polymer containing one or more

The more amine functional group and / or one or more phosphine functional group allows to control the rate at which the coating dissolves or erodes in seawater. Preferably, the counterions contain anionic residues of one or more acids with aliphatic hydrocarbon groups containing from 5 to 50 carbon atoms, more preferably from 6 to 50 carbon atoms, even more preferably from 6 to 20 carbon atoms. The counterion, for example, contains an anionic rosin residue or other rosin derivative material.

[0033] The antifouling composition of the present invention comprises a rosin material as a binder as an addition to the polymer with amine salt functional groups and / or phosphine salt functional groups associated (as side groups) with the polymer backbone, said salts containing , as a counterion, an anionic acid residue having an aliphatic, aromatic or alikloaryl hydrocarbon group of at least 5, preferably at least 6 carbon atoms. Rosin is not a substance that creates very good coatings and it is known that other coating-forming resins are added to rosin based antifouling paints. Consequently, the antifouling coating composition of the present invention comprises rosin material as a binder (optionally, the rosin may be present as a counterion in the polymer containing salt amine functional groups and / or salt phosphine functional groups), preferably further comprising non-hydrolyzing, insoluble water-forming polymer. The ratio of rosin binder to polymer salt with amine functional groups and / or phosphine functional groups of salt and optionally one or more other film-forming resin affects paint film strength and / or rosin-based paint matrix erosion.

[0034] According to a preferred embodiment of the present invention, the antifouling paint comprises a binder being a mixture of rosin material and an auxiliary film-forming resin in a weight ratio of 20:80 to 95: 5, wherein the auxiliary film-forming resin contains 20-100% by weight of film-forming polymer (A) . which is a polymer with salt groups having amine salt functional groups and / or phosphine salt functional groups associated (as side groups) with the polymer backbone, said salt groups containing counterions in the form of anionic acid residues aliphatic, aromatic or alkylaryl hydrocarbon groups containing at least 5, preferably at least 6 carbon atoms and up to 80% non-hydrolyzing, water-insoluble film-forming polymer (B).

[0035] The rosin material that is added as a binder to the composition comprising a polymer with amine functional salt groups and / or phosphine salt groups, is preferably a rosin, more particularly an extraction rosin, or alternatively tall rosin or a distillation rosin. The main chemical component of rosin is abietic acid. The rosin may be of any grade commercially available, preferably that sold as WW (balsamic) rosin. The rosin material may alternatively be a rosin derivative, for example maleic or fumaric acid-modified rosin, hydrogenated rosin, formylated rosin or polymerized rosin, or a rosin salt with a metal such as calcium, magnesium, copper or zinc rosin.

[0036] The non-hydrolyzing, water-insoluble film-forming polymer (B) is, for example, a vinyl ether polymer such as poly (vinyl alkyl ether) or a vinyl alkyl ether copolymer with

EP 1 753 829 vinyl acetate or vinyl chloride, an acrylic ester polymer such as a homopolymer or copolymer of one or more alkyl acrylate or methacrylate, which preferably contains from 1 to 6 carbon atoms in the alkyl group and may contain a comonomer such as acrylonitrile or styrene, or a polymer vinyl acetate such as poly (vinyl acetate) or a copolymer of vinyl acetate and vinyl chloride. The polymer (B) is alternatively a polyamine, in particular a polyamide with plasticizer properties such as fatty acid polyamide or polyamide sold under the trade name "Santiciser".

[0037] We have found that the paints of the present invention exhibit an optimal combination of film-forming and eroding properties when a non-hydrolyzing, water-insoluble film-forming polymer (B) is present in the composition. Most preferably, the weight ratio of rosin to the total amount of auxiliary film-forming resin is from 25:75, 50:50 or 55:45 to 80:20. The hydrolysing or dissociative film-forming polymer (A) preferably comprises at least 30, most preferably at least 50 to 80 or 90% by weight of the auxiliary film-forming resin, while the non-hydrolyzing water-insoluble polymer (B) constitutes the remainder.

[0038] The rosin and polymers forming the auxiliary film-forming resin are mixed in a conventional solvent that is at least part of the paint solvent, for example, in an aromatic hydrocarbon such as xylene, toluene or trimethylbenzene, in an alcohol such as n-butanol, in an ether alcohol such as butoxyethanol or methoxypropanol , in an ester such as butyl acetate or isoamyl acetate, in an ether ester such as ethoxyethyl acetate or methoxypropyl acetate, in a ketone such as methyl isobutyl ketone or methyl isoamyl ketone, in an aliphatic hydrocarbon such as white spirit, or in a mixture of two or more of the solvents mentioned.

[0039] The antifouling paint of the present invention, both with and without rosin, includes a non-polymeric plasticizer. This type of plasticizer may be present, for example, in amounts up to 50% by weight based on the total amount of polymeric binder, most preferably at least 10% to 35% by weight based on the total amount of polymeric binder. Examples of this type of plasticizer are phthalate esters such as dibutyl phthalates, butyl benzyl phthalate or dioctyl phthalates, phosphate triesters such as tricresyl or tris (isopropyl) phenyl phosphate, or chlorinated paraffins.

[0040] The biocidal component is usually a biocide relative to aqueous organisms or a pigment, or a mixture of said. The biocide and / or pigment can be mixed with the binder using conventional paint mixing techniques. The coating composition preferably has a pigment volume concentration of, for example, 15 to 55%.

[0041] Where the biocidal component of marine organisms is a pigment, the pigment may consist of a metal-containing pigment, for example a metal-containing pigment having a sea water solubility of from 0.5 to 10 ppm by weight. Examples of such pigments that also behave as aqueous biocides include zinc and copper compounds such as cuprous oxide, cuprous thiocyanate, cuprous sulfate, zinc ethylene (dithiocarbamate), zinc dimethyl (dithiocarbamate), zinc pyrithione, copper pyrithione, diethyl dithiocarbamate zinc, copper rosin or cuprous ethylene (dithiocarbamate). Other sparingly soluble pigments showing a 0.5 to 10 ppm sea water solubility include barium sulfate, calcium sulfate, dolomite, and zinc oxide. It is possible to use a mixture of hardly soluble pigments: for example cuprous oxide, cuprous thiocyanate or zinc ethylene (dithiocarbamate), which are highly effective

Due to biocidal pigments, they can be mixed with zinc oxide, which is not effective as a biocide, but dissolves slightly faster in seawater. Metallic copper can exist as an aqueous biocide, for example in the form of flakes or powder.

[0042] The antifouling coating composition may consist of a biocide-free marine metal component, i.e. a biocidal component which is a biocide but is not a pigment. Examples of these types of compounds are tetramethylthiuram disulfide, methylene bis (thiocyanate), captan, triphenylboron and pyridine complex, substituted isothiazolone such as 4,5,-dichloro-2-noctyl-4-isothiazolin-3-one, 2-methylthio-4- t-butylamino-6-cyclopropylamino-s-triazine, N-3,4-dichlorophenylN ', N'-dimethylurea ("Diuron"), 2- (thiocyanomethylthio) benzothiazole, 2,4,5,6-tetrachloroisophthalonitrile, dichlorofluanide, tolylfluanid, 2- (p-chlorophenyl-3-cyano-4-bromo-5-trifluoromethylpyrrole, 3-benzo (b) thieno-2-yl-5,6-dihydro-1,4,2-oxathiazine, 3-butyl-5- (dibromomethylidene) -2 (5H) -furanone, and 2,3-oxide , 6-tetrachloro-4- (methylsulfonyl) pyridine, 5-methyl-2- (1-methylethyl) cyclohexanol (L-menthol), menthol propylene glycol carbonate. This type of metal-free biocide is used as the only biocide in copper-free coatings, or even in metal-free or pigment-free anti-fouling coatings.

[0043] Optionally, the antifouling composition contains one or more acid-functionalized biocides, for example (9E) -4- (6,10-dimethylocta-9,11-dienyl) furan-2-carboxylic acid and p- (sulfoxy) cinnamic acid (zeric acid). This type of metal-free acid-functionalized biocide (s) (or mixture) is used as the only biocide in a copper-free coating, or even in a metal-free or pigment-free anti-fouling coating.

[0044] Alternatively or additionally, the acid-functionalized biocide is introduced into the polymer containing amine salt function groups and / or phosphine salt function groups, i.e. one or more counterion in the polymer is the acid residue of the acid functionalized biocide. In cases where a sufficient amount of acid-functionalized biocide is introduced into the polymer containing salt amino groups and / or phosphine salt groups, no separate biocidal component is required.

[0045] In addition to the component with biocidal properties, which is usually a biocide for aqueous organisms or a pigment or mixture of said or biocide incorporated into the polymer, the coating composition contains (other) pigments. For example, pigments that do not react with seawater and may be highly insoluble in seawater (solubility below 0.5 ppm by weight) are titanium dioxide or iron oxide or an organic pigment such as phthalocyanine or azo pigment. These types of highly insoluble pigments are preferably used in amounts corresponding to less than 60% by weight based on the total amount of pigment paint components, most preferably less than 40%.

[0046] The coating composition may further contain other additives, for example conventional thickeners, in particular thixotropes such as silica or bentonite and / or stabilizers, for example zeolites or aliphatic or aromatic amines such as dehydroabietylamine.

The invention will be explained with reference to the following examples. The examples are intended to illustrate the invention and should not be construed as limiting to any scope of the invention.

EP 1 753 829

Example 1 (Preparation of palmitate protected monomer) [0048] To obtain the N- [3- (dimethylammonium) propyl] methacrylamide palmitate salt, N- [3- (dimethylammonium) propyl] methacrylamide was reacted with palmitic acid as described below.

[0049] N- [3- (dimethylammonium) propyl] methacrylamide (20g, 0.1175 mol) was dissolved in methanol (400 mL) and placed in a 1L three-necked round bottom flask. Solid palmitic acid (30.13g, 0.1175 mol) was added to the stirred solution using a powder funnel and passing a constant stream of N2. The reaction mixture was stirred overnight at room temperature.

[0050] The colorless liquid was filtered to remove any residual insoluble impurities and the solvent was evaporated under reduced pressure. The resulting viscous liquid was analyzed¹H NMR and used without further purification.

[0051] The above-described experiment was performed under conditions in which such a reaction is routinely carried out. Changing reaction conditions are possible. For example, an alternative solvent such as ethanol, propanol, isopropanol, butanol, or mixtures thereof with xylene may be used to obtain monomer solutions that can be used directly (without isolation) in the polymerization step. In addition, the reactions can be carried out at elevated temperatures to reduce its duration.

Example 2 (preparation of abietic acid protected monomer) (rosin) [0052] To obtain the rosin salt of N- [3- (dimethylammonium) propyl] methacrylamide, N- [3- (dimethylammonium) propyl] methacrylamide was reacted with abietic acid as described below way.

[0053] N- [3- (dimethylammonium) propyl] methacrylamide (20g, 01175 mol) was dissolved in methanol (400 mL) and placed in a 1L three-necked round bottom flask. Solid abietic acid (35.54g, 0.1175 mol) was added to the stirred solution using a powder funnel and passing a constant stream of N2. The reaction mixture was stirred overnight at room temperature.

[0054] The straw liquid was filtered to remove any residual insoluble impurities and the solvent was evaporated under reduced pressure. The resulting dark viscous liquid was analyzed¹H NMR and used without further purification.

Example 3 (polymer preparation) [0055] The N- [3- (dimethylammonio) propyl] methacrylamide palmitate salt of Example 1 was polymerized with isobornylmethacrylate (iBoMA) (20:80) so that a 50% polymer solution was obtained solids.

[0056] The prepared initial solution contained N- [3- (dimethylammonio) propyl] methacrylamide palmitate (50.14 g, 0.1175 mol) in a mixture (3: 1) xylene: butanol (50 g), iBoMA (104.50 g, 0.47 mol), and 2,2'-azobis- (2-methylbutyronitrile) AMBN initiator (1.13 g, 0.0059 mol, 1 mol%). The stock solution was added dropwise over 3½ hours, mechanically stirring, under N2 atmosphere, to a reaction vessel containing a mixture (3: 1) xylene: butanol (156 g) at 85⁰C. After the monomer addition was completed, the temperature was raised to 95 ⁰C and the amount of AMBN added (0.56 g, 0.0029 mol) was increased. The reaction was carried out at elevated temperature for 1 hour. The polymer solution was transferred to a vessel and allowed to cool.

[0057] The above-described experiment was carried out under conditions where such a reaction is routinely carried out, however, changes in said conditions are possible. It is possible to use alternative solvents or solvent mixtures containing solvents for typical paints. other

The comonomers are, for example, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isobornyl acrylate, styrene, and other vinyl monomers. The monomer ratio may also change. Preferably, the amino acid salt monomer is present in amounts of 5 to 40 mol%, more preferably 10 to 30 mol%. The viscosity of the polymer solutions was such that a material could be prepared with a percentage of solids in the range of 45-65%.

Example 4 (coating composition) [0058] The following materials were mixed in the amounts given in wt.% Using a high speed dispersing device to produce the copper-containing antifouling paints of the invention.

<td>Name</td><td>Description</td><td>Dry volume video</td><td>% by weight</td>

<td>Resin protected palmitate</td><td>Resin solution</td><td> 21.61</td><td> 16.37</td>

<td>hydroquinone</td><td>Inhibitor</td><td> 0.24</td><td> 0.10</td>

<td>Tixogel MP®</td><td>coagulant organokrzemianowy</td><td> 2.42</td><td> 1.36</td>

<td>Silica-Wacker HDKN20®</td><td>thixotrope</td><td> 1.47</td><td> 1.01</td>

<td>xylene</td><td>Solvent</td><td> -</td><td> 3.05</td>

<td>Hansa-Scarlet RN-C®</td><td>Pigment</td><td> 5.10</td><td> 2.27</td>

<td>Copper Omadine®</td><td>biocide</td><td> 6.77</td><td> 3.89</td>

<td>Zinc oxide</td><td>Pigment</td><td> 6.76</td><td> 11.63</td>

<td>Cuprous oxide</td><td>biocide</td><td> 20.25</td><td> 36.73</td>

<td>Lutonal A25® (polyvinyl ether)</td><td>plasticizer</td><td> 11.93</td><td> 3.54</td>

<td>Metyloizoamyloketon</td><td>Solvent</td><td> -</td><td> 2.27</td>

Example 5 (copper-free coating composition) [0059] The following materials were mixed in the amounts given in wt.% Using a high speed dispersing device to produce copper-free antifouling paints according to the invention.

<td>Name</td><td>Description</td><td>Dry volume video</td><td>% by weight</td>

<td>Resin protected with palmitate</td><td>Resin solution</td><td> 43.24</td><td> 36.29</td>

<td>xylene</td><td>Solvent</td><td> -</td><td> 5.09</td>

<td>Bentone SD1®</td><td>coagulant organokrzemianowy</td><td> 1.01</td><td> 0.52</td>

EP 1 753 829

<td>Silica-Wacker HDKN20®</td><td>thixotrope</td><td> 0.68</td><td> 0.52</td>

<td>Anti-Terra 203®</td><td>Dispersing agent</td><td> 0.76</td><td> 0.46</td>

<td>Irgarol 1051®</td><td>biocide</td><td> 12.94</td><td> 4.93</td>

<td>Zinc oxide</td><td>Pigment</td><td> 21.45</td><td> 40.88</td>

<td>Zinc Omadine®</td><td>biocide</td><td> 6.33</td><td> 3.91</td>

<td>Lutonal A25® (polyvinyl ether)</td><td>plasticizer</td><td> 10.81</td><td> 3.56</td>

<td>Titanium dioxide (Rutile)</td><td>Pigment</td><td> 2.77</td><td> 3.84</td>

Example 6 (Copper-free coating composition) [0060] The following materials were mixed in the amounts given in wt.% Using a high speed dispersing device to produce copper-free antifouling paints according to the invention.

<td>Name</td><td>Description</td><td>Dry volume video</td><td>% by weight</td>

<td>Resin protected rosinate</td><td>Resin solution</td><td> 43.24</td><td> 36.64</td>

<td>xylene</td><td>Solvent</td><td> -</td><td> 19.92</td>

<td>Bentone SD1®</td><td>coagulant organokrzemianowy</td><td> 1.01</td><td> 0.59</td>

<td>Silica-Wacker HDKN20®</td><td>thixotrope</td><td> 0.68</td><td> 0.59</td>

<td>Anti-Terra 203®</td><td>Dispersing agent</td><td> 0.76</td><td> 0.54</td>

<td>Boracide P®</td><td>biocide</td><td> 20.36</td><td> 9.32</td>

<td>Zinc oxide</td><td>Pigment</td><td> 12.22</td><td> 26.97</td>

<td>Zinc Omadine®</td><td>biocide</td><td> 8.14</td><td> 5.82</td>

<td>Lutonal A25® (ether ethyl polyvinyl)</td><td>plasticizer</td><td> 10.81</td><td> 4.12</td>

<td>Titanium dioxide (Rutile)</td><td>Pigment</td><td> 2.77</td><td> 4.45</td>

Example 7 (copper-free coating composition) [0061] The following materials were mixed in the amounts given in wt.% Using a high speed dispersing device to produce copper-free antifouling paints according to the invention.

<td>Name</td><td>Description</td><td>Dry volume video</td><td>% by weight</td>

EP 1 753 829

<td>Resin protected rosinate</td><td>Resin solution</td><td> 39.02</td><td> 31.88</td>

<td>xylene</td><td>Solvent</td><td> -</td><td> 13.19</td>

<td>Bentone SD1®</td><td>coagulant organokrzemianowy</td><td> 0.91</td><td> 0.57</td>

<td>Silica-Wacker HDKN20®</td><td>thixotrope</td><td> 0.61</td><td> 0.57</td>

<td>Distillation rosin</td><td>Rosin</td><td> 9.76</td><td> 6.75</td>

<td>Anti-Terra 203®</td><td>Dispersing agent</td><td> 0.69</td><td> 0.51</td>

<td>Econea 028®</td><td>biocide</td><td> 22.05</td><td> 15.90</td>

<td>Zinc oxide</td><td>Pigment</td><td> 7.35</td><td> 17.01</td>

<td>Zinc Omadine®</td><td>biocide</td><td> 7.35</td><td> 5.51</td>

<td>Lutonal A25® (polyvinyl ether)</td><td>plasticizer</td><td> 9.76</td><td> 3.89</td>

<td>Titanium dioxide (Rutile)</td><td>Pigment</td><td> 2.50</td><td> 4.21</td>

Example 8 (Zinc and Copper Free Coating Composition) [0062] The following materials were mixed in the amounts given in wt% using a high speed dispersing device to produce the zinc and copper free anti-fouling paints of the invention.

<td>Name</td><td>Description</td><td>Dry volume video</td><td>% by weight</td>

<td>Resin protected with palmitate</td><td>Resin solution</td><td> 34.61</td><td> 28.87</td>

<td>xylene</td><td>Solvent</td><td> -</td><td> 4.63</td>

<td>Tixogel MP®</td><td>coagulant organokrzemianowy</td><td> 1.43</td><td> 1.01</td>

<td>Silica-Wacker HDKN20®</td><td>thixotrope</td><td> 0.35</td><td> 0.30</td>

<td>Sea-Nine 211®</td><td>biocide</td><td> 6.89</td><td> 9.94</td>

<td>Preventol A5®</td><td>biocide</td><td> 8.69</td><td> 5.12</td>

<td>Iron oxide (Bayferrox Red 130BM®)</td><td>Pigment</td><td> 3.32</td><td> 6.53</td>

<td>Lutonal A25® (ether ethyl polyvinyl)</td><td>plasticizer</td><td> 8.65</td><td> 3.23</td>

<td>Dolomite Microdol H. extra®</td><td>extender</td><td> 36.06</td><td> 40.36</td>

EP 1 753 829