HK1023140A - Antifouling paints - Google Patents

Description

Antifouling paint

The invention relates to a composition for producing an antifouling coating, comprising an organopolysiloxane as binder and a biocide as active substance.

Antifouling coatings are used to protect objects from microbial growth, particularly for ships, screens, fish nets, buildings, dock equipment, communication equipment and objects that come into contact with seawater or brackish water.

The growth of microbial growth is a serious problem, particularly in relation to ships, because, for example, an increase in frictional resistance results, with a consequent increase in energy consumption and frequent need for maintenance in dry docks, with considerable increase in operating costs. For this reason, antifouling coatings have long been used to prevent infestation by algae, barnacles, tubeworms, midges or other marine organisms.

Antifouling coatings can be distinguished essentially by comprising biocides and by not comprising biocides.

The biocide-free antifouling coating has anti-adhesion properties, i.e. the aim is to prevent the attachment of marine organisms by physical means. For example, US-a 5298060 describes a system based on a combination of silicone liquid and silicone polymer. However, biocide-free antifouling paints have limited effectiveness, so that mechanical cleaning of ship hulls or underwater structures is required in a relatively short time.

Also known are antifouling coatings containing biocides (US-A4769398). Biocides can kill growth-forming organisms. Typical antifouling biocides are organotin compounds or also compounds of copper, antimony and bismuth. A disadvantage of these biocides is their poor environmental compatibility. Antifouling biocides containing heavy metals are particularly problematic because they cause contamination of seawater and the seabed, especially in harbour areas. On the other hand, the clean organic biocides also mentioned in US-A4769398 do not have good long-term action, apparently because the active substance has decomposed prematurely in the coating.

It is therefore an object of the present invention to provide a highly effective antifouling paint having good long-term action and improved environmental compatibility.

It has now surprisingly been found that antifouling coatings which do not contain heavy metal biocides can provide antifouling properties significantly, while having good long-term action and improved environmental compatibility, if organopolysiloxanes are used as binders in antifouling coatings.

The invention therefore provides compositions which contain a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.

In the antifouling coating of the invention, the good antifouling effect of the combination of the heavy metal-free biocide and the organopolysiloxane as binder is apparently produced by the synergistic effect of the biocidal effect of the biocide and the physical effect of the organopolysiloxane.

Organopolysiloxanes, such as silicones, silicone rubber systems, organomodified polysiloxanes such as polyether siloxanes, epoxy-functional or amino-functional siloxanes and silicone acrylates and/or silicone copolymers, which are preferably used according to the invention, have an antisticking effect on the one hand on account of their hydrophobic surface. This effect reduces the growth of algae, barnacles, tubeworms, midges or other marine organisms on the surfaces of ship hulls and underwater structures. At the same time, the hydrophobic polymer matrix of the invention gives the heavy metal-free biocide contained therein an improved long-term action. This relates in particular to the biocides which are decomposable in seawater used in the preferred embodiment.

In a particularly preferred embodiment of the invention, the long-term action can be further increased by additional microencapsulation of the heavy metal-free biocide.

Suitable biocides are preferably heavy metal-free trehalates, fungicides, insecticides, molluscicides and bactericides such as

Triazoles: penconazole, bromuconazole, cyproconazole, diclorotriazolol, diniconazole, hexaconazole, metconazole, penconazole, propiconazole, tebuconazole, aminotriazole, azocyclotin, epoxiconazole, bitertanol, difenoconazole, benzonitrile, fenchlorazole, fennethanil, fluqinconazole, flusilazole, flutriafol, imibenconazole, cloxaphos, myclobutanil, paclobutrazol, (±) -cis-1- (4-chlorophenyl) -2- (1H-1,2, 4-triazol-1-yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triafol, triflumizole, triticonazol, uniconazol and metal salts and acid adducts thereof.

An azole: imazalil, pefurazoate, prochloraz and triflumizole.

Thiazole carboxylic acid anilides, such as 2 ', 6 ' -dibromo-2-dimethyl-4-trifluoromethoxy-4 ' -trifluoromethyl-1, 3-thiazole-5-carboxylic acid anilide and metal salts and acid adducts thereof.

Succinate dehydrogenase inhibitors such as: benfurazolin, furacanbanil, cyclafluramid, dressing amine, seedvax, tiadinil, picocarbolid, oxycarboxin, Shirlan, mebenil, iodocarbox, flutolanil (montut);

naphthalene derivatives such as: terbinafine, naftifine, butenfine; sulfonamides such as dichlofluanid, tolylfluanid, folpet; carbendazim, captan; benzoxazoles such as carboxin, benomyl, furathiocarb, fuberidazole, thiophanate-methyl, thiabendazole or salts thereof; morpholine derivatives such as morpholine, fenpropimorph, falimorph, dimethomorph, moroxydine; aldimorph, benoxanthine and their salts with aryl sulfonic acids such as p-toluenesulfonic acid and p-dodecylbenzenesulfonic acid; dithiocarbamates such as thiabendazole, ferbam, bisultant, mancozeb, maneb, metam, metiram, thiram, zineb, ziram benzothiazoles such as 2-mercaptobenzothiazole; benzamides such as 2, 6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; boron compounds such as boric acid, boric acid esters, borax; formaldehyde and formaldehyde donor compounds such as benzyl alcohol mono (poly) hemiacetal, oxazolidines, hexahydro-S-triazine, N-hydroxymethylchloroacetamide, polyoxymethylene, nitropyridine, 1,4,5, 6-tetrahydro-4, 6-dioxo-1, 3, 5-triazine-2-carboxylic acid, teclofalam; tris-N- (cyclohexyldiazepino) -aluminum; n-methylisothiazol-3-one, 5-chloro-N-methylisothiazol-3-one, 4, 5-dichloro-N-octylisothiazol-3-one, N-octyl-isothiazol-3-one, 4, 5-trimethylene-isothiazolinone, 4, 5-benzisothiazolinone; aldehydes such as cinnamaldehyde, formaldehyde, glutaraldehyde, β -bromocinnamaldehyde; thiocyanates such as thiocyanomethylthio benzothiazole, methylene bisthiocyanate, and the like; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride; iodine derivatives such as diiodomethyl p-tolylsulfone, 3-iodo-2-propynol, 4-chlorophenyl-3-iodopropynylphenylmethylal, 3-bromo-2, 3-diiodo-2-propenylethylcarbamate, 2,3, 3-triiodoallyl alcohol, 3-bromo-2, 3-diiodo-2-propenol, 3-iodo-2-propynyl-n-butylcarbamate, 3-iodo-2-propynyl-n-butylurea, 3-iodo-2-propynyl-n-hexylcarbamate, 3-iodo-2-propynyl cyclohexylcarbamate, 3-iodo-2-propynyl phenylcarbamate; phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3, 5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol, and alkali metal salts and alkaline earth metal salts thereof.

Microbicides having an active halogen group such as chloroacetamide, N-hydroxymethylchloroacetamide, bronopol, bronidox, protecmers such as 2-bromo-2-nitro-1, 3-propanediol, 2-bromo-4' -hydroxyacetophenone, 2-dibromo-3-nitrilopropionamide, 1, 2-dibromo-2, 4-dicyanobutane, beta-bromo-beta-nitrostyrene; pyridines such as 1-hydroxy-2-pyridinethione (and its Na, Fe, Cu, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyridinemethanol, mepanipyrim, dipyrithione; dialkyldithiocarbamates such as Na salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, N-methyl-dithiocarbamate; nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyanodithioiminocarbamate; quinolines such as 8-hydroxyquinoline and copper salts thereof; mucochloric acid, 5-hydroxy-2 (5H) furanone; 4, 5-dichlorodithiazolidinone, 4, 5-benzodithiazolidinone, 4, 5-trimethylenedithiazolinone, 4, 5-dichloro- (3H) -1, 2-dithiol-3-one, 3, 5-dimethyl-tetrahydro-1, 3, 5-thiadiazin-2-thione, N- (p-chlorobenzoylethyl) hexa-ammonium chloride, potassium N-hydroxymethyl-N' -methyl-dithiocarbamate, 2-oxo-2- (4-hydroxy-phenyl) hydroxamic acid chloride, phenyl 2-chloro-cyano-vinylsulfone;

in addition, highly effective compositions can also be prepared with the following active substances: fungicides: (E) -methoxyimino [ alpha- (o-tolyloxy) -o-tolyl ] acetic acid methyl ester, (E) -2- {2- [ 6- (2-cyanophenoxy) -pyrimidin-4-yl-oxy ] phenyl } -3-methoxyacrylate methyl ester, acetoacs, 2-butylamine, ampropyfos, dichlofluanid, benalaxyl, butylpyrimidine sulfonate, mefenamic acid, dicyclopentadine, difluoramide, cymoxanil, dazomet, nicum, clotrimazole, diethofencarb, methamidol, diocab, dithianon, dodine, dixolone, edifenprox, pyrimethamine, clomazole, diclozopyrimidine, pefurazone, fenpyrad, fentin, pyriizone, fluazinam, fluocinolone, flutriafol, fosetyl, tetrachlorophthalide, furalazine, hydroxyisoxazole, iprobenfos, isoprothiolane, propamol, clozapyr, fluazid, flu, Iprodione, isoprothiolane, metalaxyl, sulbencarb, nitrotha 1-isoproyl, fluoropyrimidinol, ofuramide, oxazamide, perflurazoate, pencycuron, phosdiphen, pimaricin, pyridinin, dimetachlone, propamocarb, propineb, procymidone, pyroquintozene, tar, tetrachloronitrobenzene, thifluzalone, thiophanate-methyl, tolclofos-methyl, pyrazoxazine, trichlamide, triazamate, zindol, vinclozolin.

Insecticide:

phosphates such as ethidium glutethionate, α -1 (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, coumaphos, phoxim II, dinoflagellate, dichlorvos, dimethoate, ethoproxil, fenbutatin, fenthion, heptanophos, malathion, methylmercaptothion, vothion, phoxim, ethylpyrimidinethion, pirimiphos, profenofos, prothiofos, meprobamate, triazophos and trichlorfon;

carbamates such as aldicarb, bendiocarb, alpha-2- (1-methylpropyl) -phenylmethylcarbamate, butoxycarb, butoxycarbxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, methiocarb, pirimicarb, merfentraway, propoxur, and thiodicarb; organosilicon mixtures, preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ethers such as dimethyl- (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (dimethylphenyl) silyl-methyl-2-phenoxy-6-pyridylmethyl ethers such as, for example, dimethyl (9-ethoxy-phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [ (phenyl) -3- (3-phenoxyphenyl) propyl ] -dimethyl (dimethyl) silanes such as, for example, (4-ethoxyphenyl) - [ 3- (4-fluoro-3-phenoxyphenyl-propyl) dimethyl-silane, silafluofen;

pyrethroids such as allethrin, pyrethroids, esbiothrin, byfenthrin, cycloprothrin, cyfluthrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2, 2-dimethyl-3- (2-chloro-2-trifluoro-methylvinyl) cyclopropanecarboxylate, fenpropathrin, fenfluthrin, fenvalete, flucythrinate, flumethrin, fluvalinate, permethrin, and tralomethrin;

nitroimides and nitromethylenes, e.g. 1- [ (6-chloro-3-pyridyl) -methyl ] -4, 5-dihydro-N-nitro-1H-pyrim-azol-2-amine (imidacloprid), N- [ (6-chloro-3-pyridyl) methyl ] -N²-cyano-N¹-methylacetamide (NI-25);

abamectin, AC303, 630, acephate, fluthrin, gossypol, aldoxcarb, amethomide, azamethiphos, bacillus thuringiensis, cyromazine, phosmet, pyrazothion, phosphine, prallethrin, propaphos, propentamphos, pomade, phosphamidon, pyrethrum, pyridaben, pyridaphenthion, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, sulfotepa, sulfur fluoride, tar, tefluthrin, disulfoton, tebuthion, methidathion, tetramethrin, O-2-tert-butyl-pyrimidin-5-yl-O-isopropyl-phosphorothionate, thiocyclam, ketoxycarb, methidathion, tetrabromthrin, dimefluthrin, trimethacarb, fenthion, thiodicarb, valicarb, lachlorfenpyr, lacarb, propathrin, propargyl, cyfluthrin, pyrethrum, cyhalothrin, MERBIOAllethrin (S) cyclopentenyl isomer, bromophos-ethyl, buprofezin, cadusafos, calcium polysulphide, trithione, badan, shinomethionat, chlordane, chlorfenvinphos, chlormephos, chlornitromethyl, chlorpyrifos, cyanophos, alpha-cyfluthrin, alpha-cypermethrin, cyenophenothrin, cyenophos, cyromazine, dazomet, DDT, demeton-S-methysulphos, chlordiazuron, dialifos, profos, flufenoxuron, dinotefuran, deobenazofos, diaxacarb, fosetyl, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethion, ethofenprox, fenpropathrin, benuron, chlorphenuron, chlorpheniram, chlorphenuron, chlorp, Metam, Metarthizium, anisopliae, chlorfenvinphos, methamidophos, methidathion, methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metalloparb, methamphetamine, monocrotophos, vozapyr, Neodiprion serotifer NPV, nicotine, oxadiumyl, SULPHUS, pentachlorophenol, petroleum, phenothrin, phenthon, phorate;

a molluscicide:

fentiniacetate, snaila powder, methiocarb, bexaprid, thiodicarb, trimethacarb;

algicide:

antifungal phenol, endothal, fentinacetate, qinocamine;

herbicide:

diuron, dichlorophen, endothal, fentinacat, qinocamine.

Suitable biocides are preferably algicides such as diuron, dichlorophen, endothal, fentinoacetate, qinocladamine, molluscicides such as fentin acetate, metalaxyl, methiocarb, conchiolide, thiodicarb, trimethacarb, fungicides such as dichlofluanid, tolylfluanid, idopropyl buticamate, fluofolpet and azoles such as 2- (N, N-dimethylaminothiocarbonyl thio) -5-nitrothiazolyl, tetrabutyldistan, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1, 3, 5-triazine, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, 2,4,5, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide, 2,4, 6-trichloromaleimide, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) -pyridine, diiodomethylparatryl sulfone, thiabendazole, tetraphenylboropyridine salt, sodium salt of 2-pyridylthio-1-oxide.

Other preferred biocides of the invention are benzothiophene-2-carbonamides S, S-dioxides of the formula IWherein

R¹Represents optionally substituted alkyl, represents alkenyl or alkynyl, represents in each case optionally substituted cycloalkyl or cycloalkylalkyl, or represents in each case optionally substituted aralkyl, aralkenyl, aralkynyl or aryl,

R²represents hydrogen or represents optionally substituted alkyl or

R¹And R²And the nitrogen atom to which they are attached together represent an optionally substituted heterocyclic ring, and

R³、R⁴、R⁵and R⁶Independently of one another, each represents hydrogen, halocyano, nitro, alkyl, alkoxy, thioalkyl, haloalkyl, haloalkoxy or halothioalkyl.

In particular the compound N-cyclohexylbenzothiophene-2-carboxamide S, S-dioxide.

Particularly good results can also be obtained by combinations of active substances, preferably specific biocide combinations.

Particularly preferred are those biocides which are decomposable.

The term "decomposable" for the purposes of the present invention refers to those biocides which have a half-life in seawater at 25 ℃ of less than 180 days, preferably less than 90 days. The mechanism of the decomposition reaction is not critical to the effect of the present invention. It may be chemical decomposition by, for example, hydrolysis or oxidation, photochemical decomposition, or biological decomposition by microorganisms.

Examples of suitable decomposable active substances are, for example, phenoxyacetic acids, ureas, thioureas, thiocarbamates, sulfonamides and halogenated aromatic compounds. Preferred active substances are:

the long-term action of the biocide is preferably enhanced by microencapsulation. Suitable materials for biocide microencapsulation are the known materials used for this purpose, in particular polymers. Examples of suitable polymers are polyesters, natural and synthetic polyamides, melamine resins, polyurethanes, polyureas, polysiloxanes, poly (meth) acrylates and copolymers of (meth) acrylic acid and (meth) acrylates. In many cases, it is advantageous to use crosslinked polymers. Gelatin is particularly suitable as a natural polyamide. It is used in particular as coacervate and complex coacervate. The gelatin-containing complex coacervates used in the present invention specifically employ a combination of gelatin and synthetic polyelectrolytes. Suitable synthetic polyelectrolytes are copolymers which incorporate units of, for example, maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide. The gelatin-containing microcapsules may be crosslinked using conventional crosslinking agents such as, for example, formaldehyde or glutaraldehyde.

The microencapsulated biocide may be in the form of individual biocide particles encapsulated by a polymer. They may also be polymer particles in which a large number of biocide particles are contained, or polymer particles in which the biocide is present dispersed in the molecular state. Microencapsulation of the isolated biocide particles can be carried out by known methods, for example, by applying the polymer in solution to the biocide particles by precipitation of the polymer or by evaporation of the solvent. The polymers can also be formed on the surface of the biocide by assembly reactions, such as polyaddition, polyaddition or polycondensation.

The preparation of polymer particles containing a plurality of biocide-containing particles can be carried out, for example, by melt compounding followed by comminution. Another very suitable method for preparing biocide-containing polymer particles is bead addition polymerization. In this method, a liquid mixture of monomer and biocide is dispersed into small droplets and solidified, giving spherical particles in which the active substance is contained. Suitable monomers for the preparation of the bead addition polymers containing biocides are, for example, the following monofunctional monomers and polyfunctional monomers which are customary as crosslinkers: styrene, vinyltoluene, chlorostyrene, chloromethylstyrene, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, divinylbenzene, diethylene glycol divinyl ether, 1, 7-octadiene, 1, 5-hexadiene, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and methallyl methacrylate.

It has been found that antifouling coatings with bead addition polymers containing active substances permit high loadings and have very good processability.

The average particle size of the microencapsulated biocide is from 0.1 to 200. mu.m, preferably from 0.2 to 20 μm.

In microencapsulated or other forms of antifouling coating, the proportion of biocide is from 1 to 50, preferably from 2 to 40,% by weight, based on the antifouling coating.

The binder used in the antifouling paint of the invention is at least one organopolysiloxane such as silicone resins, silicone rubber systems, organically modified polysiloxanes such as polyether siloxanes, epoxy-or amino-functionalized siloxanes and silicone acrylates and silicone copolymers. However, it is also possible to use mixtures of specific polysiloxanes.

The silicone resin used is a physically dry silicone resin of the general formula (1) with a high molecular weightWherein R is¹Represents a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may carry a substituent R which is inert to water²Represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a is 0, 1,2 or 3, on average 0.75 to 1.5, and b is 0, 1,2 or 3, on average 0.01 to 0.1.

Also useful are low molecular weight alkoxy-functional silicone resins of formula (2) and mixtures of high molecular weight silicone resins and low molecular weight alkoxy-functional silicone resins.Wherein R is³Represents a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may carry a substituent R which is inert to water⁴Represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a is 0, 1,2 or 3, on average 0.75 to 1.5, and b is 0, 1,2, 3, on average 0.2 to 2.0.

The silicone rubber systems used are all prior art condensation-crosslinking or addition-crosslinking systems, such as room-temperature-crosslinking one-or two-component rubbers or vulcanizable two-component liquid rubbers. The compositions of silicone rubbers which can be used according to the invention are described, for example, in Ullmann's encyclopedia of Industrial chemistry, volume A23, 306 ff.

The organomodified polysiloxanes, which may be linear or branched polysiloxanes, may carry organic functional groups or groups arranged at the chain end and/or laterally.

The adhesive is usually processed from an organic solvent or as an aqueous dispersion. Examples of suitable organic solvents are aliphatic hydrocarbons, in particular petroleum fractions, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones and ethers.

In addition to the heavy metal-free biocides and organopolysiloxanes, the antifouling coating compositions of the invention may comprise customary auxiliaries, such as, for example, fillers, solvents, plasticizers, dyes, pigments, catalysts, inhibitors, thickeners, coating additives and/or customary dispersing or shaping auxiliaries. In addition to heavy metal-free biocides, it is of course also possible for heavy metal-containing biocides to be present, such as, for example, N- (cyclohexyldiazoniadioxy) tributyltin or K salt, bis-N- (cyclohexyldiazoniadioxy) -copper; metal soaps such as tin, copper and zinc salts of naphthenic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, phosphoric acid and benzoic acid; metal salts such as copper hydroxycarbonate, sodium dichromate, potassium chromate, copper sulfate, sodium dichromate, potassium dichromate, sodium,Copper chloride, copper borate, zinc fluosilicate and copper fluosilicate; oxides such as tributyltin oxide, CuO₂CuO and ZnO; ag, Zn or Cu containing zeolites, alone or included in a polymeric active material, although in the latter case the ecological advantages are limited.

The following examples are illustrative of the invention. However, the present invention is not limited to these examples.

Examples

Example 1

Microencapsulation of diuron (Encapsulated)

The following ingredients were weighed and added to a sand mill:

12g diuron

0.06g dispersant (Baykanol SI, Bayer Co.)

48g of 5% strength 24% by weight methacrylic acid, 36% by weight methyl

Alkaline water of a terpolymer of acrylic ester and 40% by weight of butyl acrylate

A solution, and

10g of water.

The mixture was shaken in a sand mill for 20h, during which time the particle size of diuron was reduced to 0.5 μm to 1.0. mu.m. The mixture is then acidified with 15ml of 1N HCl and heated at 60 ℃ for 1h, the solid is filtered off, washed with 30ml of water and dried under vacuum at 60 ℃. 14.2g of microencapsulated diuron were obtained.

Example 2

Microencapsulation of diuron (bead polymerization)

100g of diuron, 30g of highly dispersed silica (HDK H2000, Wacker chemical Co.), 285g of methyl methacrylate and 15g of ethylene glycol dimethacrylate were thoroughly mixed in a ball mill at room temperature for 10 hours. Subsequently, 3g of dibenzoyl peroxide were added and the resulting mixture was transferred to a 31 stirred reactor containing a 1.51 concentration of 1% aqueous base solution of a copolymer of 50% by weight of methacrylic acid and 50% by weight of methyl methacrylate (adjusted to a pH of 0.8 with NaOH). The stirring speed was set at 600rpm and maintained at a temperature of 78 ℃ for 2 hours and then at 85 ℃ for 1 hour. After cooling, the solid obtained is separated by decanting, washed several times with water and dried at 80 ℃ for 12 hours. 385g of microencapsulated diuron in the form of bead addition polymers having an average particle size of 15 μm were thus obtained.

Example 3

Microencapsulation (encapsulation) of alsystin

Example 1 was repeated with alsystin instead of diuron. 13.5g of microencapsulated alsystin were obtained.

Example 4

Coatings of the invention

2G of a dispersion consisting of 50% by weight of diuron and 50% by weight of Isopar G were dispersed in 11.67G of a silicone solution having a viscosity of 3000mPas and consisting of 77.1% by weight of a physically dry high molecular weight organopolysiloxane and 22.9% by weight of Isopar G, the dispersion being carried out with a high-speed stirrer. The dispersion was applied to a metal plate coated with an epoxy lacquer with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at 60 ℃ for 10 hours. This gives a uniform coating with a coating thickness of about 150. mu.m.

Example 5

Coatings of the invention

Some procedures were the same as in example 4. However, 50% by weight of a dispersion of alsystin in isoparG was added.

Example 6

Coatings of the invention

3G of a dispersion consisting of 33% by weight of diuron microencapsulated in example 2 and 77% by weight of Isopar G were dispersed in 11.67G of a silicone solution having a viscosity of 3000mPas and consisting of 77.1% by weight of a physically dry high molecular weight organopolysiloxane and 22.9% by weight of Isopar G, the dispersion being carried out with a high-speed stirrer. The dispersion was applied to a metal plate coated with an epoxy lacquer with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at 60 ℃ for 10 hours. This gives a uniform coating with a coating thickness of about 150. mu.m.

Example 7

Coatings of the invention

11.67G of a silicone solution having a viscosity of 3000mPas, consisting of 77.1% by weight of physically dry high molecular weight organopolysiloxane and 22.9% by weight of Isopar G, were diluted with 4G of Isopar G. 1g of diuron microencapsulated in example 1 was dispersed in this solution with a high speed stirrer. The dispersion was applied to a metal plate coated with an epoxy lacquer with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at 60 ℃ for 10 hours. This gives a uniform coating with a coating thickness of about 150. mu.m.

Example 8

Coatings of the invention

The same as in example 7. However, 1g of the microencapsulated alsystin of example 3 was dispersed in a dilute silicone solution.

Example 9

Coatings of the invention

The same as in example 7. However, a mixture consisting of 0.5g of the microencapsulated diuron of example 1 and 0.5g of the microencapsulated alsystin of example 3 was dispersed in a dilute silicone solution.

Example 10

Comparative example

11.67G of a silicone solution having a viscosity of 3000mPas, consisting of 77.1% by weight of physically dry high molecular weight organopolysiloxane and 22.9% by weight of Isopar G, were diluted with 4G of Isopar G. The resin solution was applied to a metal plate coated with epoxy varnish by means of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at 60 ℃ for 10 hours. This gives a uniform coating with a coating thickness of about 150. mu.m.

Example 11

Coatings of the invention

6g diuron, 1.8g Baysilone were mixed with a high speed mixer^Coating additive PL (available from Byer) and 0.12g Baysilone^Coating additive test product A13465 (available from Bseyer) was dispersed in 26.7g of an OH-functionalized polyoxyalkylene-polyethyl siloxane copolymer. The dispersion was mixed with 27.3g of a polyisocyanate prepolymer (Desmodur E21, available from Bseer) and the resin solution was applied to a metal plate coated with an epoxy lacquer with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at room temperature. This gives a uniform coating with a coating thickness of about 250. mu.m.

Example 12

Coatings of the invention

Same as in example 11. However, the biocide used was 6.0g alsystin.

Example 13

Coatings of the invention

Same as in example 11. However, the biocide used was 6.0g of diuron microencapsulated in example 2.

Example 14

Coatings of the invention

Same as in example 11. However, the biocide used was 6.0g of alsystin microencapsulated in example 13.

Example 15

Comparative example

Some procedures were the same as in example 11. However, no biocide was used.

Example 16

Coatings of the invention

3g of diuron were dispersed in linear alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of about 500mPas with a high-speed stirrer. The dispersion was mixed with 0.81 crosslinker C5 (available from Bsyer) and the resin solution was applied to epoxy-lacquer-coated metal sheets with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at room temperature. This gives a uniform coating with a coating thickness of about 250. mu.m.

Example 17

Coatings of the invention

Same as in example 16. However, the biocide used was 6.0g alsystin.

Example 18

Coatings of the invention

Same as in example 16. However, the biocide used was 3g of the microencapsulated diuron of example 2.

Example 19

Coatings of the invention

Same as in example 16. However, the biocide used was 3g of the encapsulated alsystin of example 3.

Example 20

Comparative example

Same as in example 16. However, no biocide was used.

Example 21

Coatings of the invention

3g of diuron dispersed in 27g of vinyl-functionalized polymethylsiloxane was mixed using a high speed stirrerIn the compound (Silopren)^Alkaline mixture H6, available from Bsyer). The dispersion is admixed with 1.81g of SiH-containing crosslinker (Silopren)^U crosslinker 830, available from Bseyer) and 0.027g Pt catalyst (Silopren)^Pt/S catalyst available from Bsyer) and coated with a doctor blade onto a metal plate coated with a [ hourglass ] epoxy lacquer to form a wet film having a thickness of 250 μm. The coating was dried at room temperature. This gives a uniform coating with a coating thickness of about 250. mu.m.

Example 22

Coatings of the invention

The same as in example 21. However, the biocide used was 3g alsystin.

Example 23

Coatings of the invention

The same as in example 21. However, the biocide used was 3g of the microencapsulated diuron of example 2.

Example 24

Coatings of the invention

The same as in example 21. However, the biocide used was 3g of the encapsulated alsystin of example 3.

Example 25

Comparative example

The same as in example 21. However, no biocide was used.

Example 26

Coatings of the invention

2g of alsystin was dispersed in 30.2g of a silicon-acrylate copolymer (Baysilon) using a high speed stirrer^Impregnant LF, available from Bsyer). The dispersion was applied to a metal plate coated with an epoxy lacquer with the aid of a doctor blade to form a wet film having a thickness of 250 μm. The coating was dried at room temperature. Thereby obtaining a coatingA uniform coating thickness of about 155 μm.

Example 27

Coatings of the invention

The same as in example 26. However, the biocide used was 2g of the encapsulated alsystin of example 3.

Example 28

Comparative example

The same as in example 21. However, no biocide was used.

Application examples 29 to 33 for testing the adhesion of marine diatoms (Pusilla, rhombohedral) on the coating according to the invention

Testing the microorganisms: diatom rhombus algae (submarine diatom)

Medium: ASW media

A culture container: conical culture bottle

The test conditions are as follows: artificial light of constant temperature 18 ℃ held in a rotary oscillator

Shaking for a long time without additional ventilation.

Evaluation: comparison of the coating of the invention with comparative example 10 and with an epoxy resin

Microbial growth on painted metal panels. Degree of growth

The following classifications are made:

+++: good and uniform breeding

++: low breeding

+: very low growth

-: has no breeding

Examples		Growth after 14 days
			29	The coating of example 4 of the invention was exposed to the above test conditions for 14 days	+
30	Same as example 29, but with the coating of the invention of example 5	+
			31	Same as example 29, but with the coating of the invention of example 9	-

32	Same as example 29, but using the coating of example 10 (comparative example)	++
			33	Epoxy resin paint coated metal plate	+++

Results using the examples:

the coating of example 4 of the invention contained an organopolysiloxane as binder and diuron as a decomposable biocide. The coating shows only very low growth (+) after 14 days of exposure to deep sea diatom algae under constant artificial light at 18 ℃, constant shaking in a rotary shaker and no external ventilation.

In example 30, the coating of the invention according to example 5 likewise shows only very low growth (+). The coating contains an organopolysiloxane as binder and alsystin as decomposable biocide.

The coating of example 9 of the invention was present without breeding (-) under the above conditions. It likewise contains an organopolysiloxane as binder and a mixture of microencapsulated diuron and microencapsulated alsystin as biocide. This is surprising, and good long-term action can be obtained with microencapsulated biocides.

The coating of comparative example 10 contained no biocide. The binder is an organopolysiloxane. In example 32, this coating showed low auxotrophy (++). On the other hand, in example 33, the metal plate coated with the epoxy resin varnish showed good uniform breeding (+++).

Claims (14)

1. A composition comprising a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.

2. The composition of claim 1, characterized in that the biocide is decomposable in seawater.

3. The composition of claim 2, characterized in that the biocide has a half-life in seawater at 25 ℃ of less than 180 days.

4. Composition according to one or more of claims 1 to 3, characterized in that the biocide is microencapsulated.

5. Composition according to one or more of claims 1 to 4, characterized in that the organopolysiloxane is a high molecular weight silicone resin of the formulaWherein R is¹Represents a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may carry a substituent R which is inert to water²Represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a is 0, 1,2 or 3, on average 0.75 to 1.5, and b is 0, 1,2 or 3, on average 0.01 to 0.1.

6. Composition according to one or more of claims 1 to 5, characterized in that the organopolysiloxane is a low molecular weight alkoxy-functional silicone resin of the formulaWherein R is³Represents a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may carry a substituent R which is inert to water⁴Represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, a being 0, 12 or 3, on average 0.75 to 1.5, and

b is 0, 1,2, 3, on average 0.2-2.0.

7. Composition according to one or more of claims 1 to 6, characterized in that the organopolysiloxane is a silicone rubber.

8. Composition according to one or more of claims 1 to 7, characterized in that the organopolysiloxane contains terminal and/or pendant organofunctional groups.

9. Composition according to one or more of claims 1 to 8, characterized in that the organopolysiloxane is a silicone copolymer system.

10. Composition according to one or more of claims 1 to 9, characterized in that it also contains inorganic pigments, preferably insoluble in seawater, organic pigments, dyes and/or customary auxiliaries such as fillers, solvents, plasticizers, catalysts, inhibitors, thickeners, coating additives and/or customary dispersing assistants.

11. Use of a) at least one organopolysiloxane and b) at least one heavy metal-free biocide for the preparation of antifouling compositions and for the production of antifouling coatings.

12. A process for the preparation of an antifouling coating, characterized in that the various ingredients used in the antifouling composition are mixed with a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.

13. An antifouling paint obtainable by the process of claim 11.

14. A process for the preparation of an antifouling coating, characterised in that a composition comprising at least one organopolysiloxane and at least one heavy metal-free biocide is applied to an article to be protected.