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EP0934367A1 - Antifouling paints - Google Patents

Antifouling paints

Info

Publication number
EP0934367A1
EP0934367A1 EP97912174A EP97912174A EP0934367A1 EP 0934367 A1 EP0934367 A1 EP 0934367A1 EP 97912174 A EP97912174 A EP 97912174A EP 97912174 A EP97912174 A EP 97912174A EP 0934367 A1 EP0934367 A1 EP 0934367A1
Authority
EP
European Patent Office
Prior art keywords
organopolysiloxane
composition according
biocides
biocide
antifouling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97912174A
Other languages
German (de)
French (fr)
Inventor
Markus Mechtel
Wolfgang Podszun
Karl-Heinz Kaesler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0934367A1 publication Critical patent/EP0934367A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the invention relates to agents for the production of antifouling coatings which contain organopolysiloxanes as binders and biocides as active ingredients.
  • the anti-fouling coatings are used to protect objects from fouling, in particular ship hulls, sieves, nets, structures, quay systems, signaling systems and objects that come into contact with sea or brackish water.
  • Biocide-free antifouling coatings have non-stick properties, i.e. the establishment of marine organisms should be physically prevented.
  • US-A 5 298 060 a system based on organosilicon liquids in
  • Antifouling coatings containing biocides are also known (US-A).
  • biocides kill the growth-forming organisms.
  • Common antifouling biocides are organic tin compounds or copper antimony and bismuth compounds. The disadvantage of these biocides is their low environmental impact. Heavy metal-containing antifouling biocides are particularly problematic since they contaminate the seawater and the
  • the object of the present invention is therefore to provide a highly effective antifouling coating with a good long-term effect and improved environmental compatibility.
  • antifouling coatings with heavy metal-free biocides have significantly improved antifouling properties combined with a good long-term effect and improved environmental compatibility if organopolysiloxanes are used as binders in the antifouling coating.
  • compositions comprising a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.
  • the good antifouling effect of the combination of heavy metal-free biocide and organopolysiloxane as a binder in the antifouling coating according to the invention is evidently caused by a synergism between the biological effect of the biocide and the physical effect of the organopolysiloxane.
  • organopolysiloxanes preferably used according to the invention such as silicone resins, silicone rubber systems, organomodified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and / or
  • Organosilicone copolymers have a non-stick effect due to their hydrophobic surface. This reduces the growth of algae, barnacles, tube worms, mussels or other marine organisms on the surface of ship hulls and underwater structures.
  • the hydrophobic polymer matrix according to the invention has the effect that the heavy metal-free biocides contained therein have an improved long-term effect. This applies in particular to the biocides which are used in the preferred embodiment and are biodegradable in seawater.
  • the long-term effect is achieved by an additional microencapsulation of the heavy metal-free
  • Biocides increased. Suitable biocides are preferably heavy metal-free algicides, fungicides, insecticides, molluscicides and bactericides such as
  • Azocyclotine epoxyconazole, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, paclobutrazole, ( ⁇ ) -cis-l- (4-chloro , 2,4-triazol-l -yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
  • Thiazole carboxanilides such as 2 , 6'-dibromo-2-methyl-4-trifluoromethoxy-4 , -trifluoromethyl-l, 3-thiazole-5-carboxanilides and their metal salts and acid adducts.
  • Succinate dehydrogenase inhibitors such as:
  • Naphthalene derivatives such as:
  • Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
  • Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; AI dimorphic, fenpropidine and their aryl sulfonic acid salts, such as p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
  • Benzothiazoles such as 2-mercaptobenzothiazole
  • Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide
  • Boron compounds such as boric acid, boric acid ester, borax;
  • Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poiy) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide,
  • Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, ⁇ -bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;
  • quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
  • Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-tri- iodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-butyl urea, 3-iodo-2-propynyl n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate;
  • Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,
  • Microbicides with activated halogen group such as chloroacetamide, N-methylolchloroacetamide, Bronopol, Bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3- nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, ⁇ -bromo- ⁇ -nitrostyrene;
  • activated halogen group such as chloroacetamide, N-methylolchloroacetamide, Bronopol, Bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3- nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, ⁇ -bromo- ⁇ -
  • Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Cu, Mn, Zn salts),
  • Tetrachloro-4-methylsulfonylpyridine pyrimethanol, mepanipyrim, dipyrithione;
  • Dialkyldithiocarbamates such as sodium salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
  • Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
  • Fthalide Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Proponomone, Pyilonium, Propyloxinone, Proamonoxin, Proiloxin, Proamonoxin, Proconoxin, Proiloxin, Proconoxin, Proamon, Pyronoxin, Proconoxin, Proamonoxin Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide,
  • Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, ⁇ -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos,
  • Etrimfos Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone;
  • Carbamates such as aldicarb, bendiocarb, ⁇ -2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb,
  • Isoprocarb methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
  • Organosilicon compounds preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxy-benzyl ether or
  • Pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
  • Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N 2 - cyano-N ⁇ methylacetamide (NI-25);
  • Preferred biocides are algicides such as diuron, dichlorophene,
  • Biocides preferred according to the invention are also benzothiophene-2-carboxamide-S, S-dioxide of the formula (I)
  • R 1 stands for optionally substituted alkyl, for alkenyl or alkynyl, for each optionally substituted cycloalkyl or cycloalkylalkyl, or for each optionally substituted aralkyl, aralkenyl, aralkynyl or aryl,
  • R represents hydrogen or optionally substituted alkyl or R 1 and R 2 together with the nitrogen atom to which they are attached represent an optionally substituted heterocycle and
  • R 3 , R 4 , R 5 and R 6 each independently represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio.
  • the compound N-cyclohexylbenzothiophene-2-carboxamide-S, S-dioxide is particularly preferred.
  • Degradable in the sense of the invention is understood to mean those biocides which have a half-life of less than 180 days, preferably less than 90 days, in sea water at 25 ° C.
  • the mechanism of the degradation reaction is not critical to the inventive effect.
  • Chemical degradation by e.g. Hydrolysis or oxidation, photochemical degradation or biodegradation by microorganisms.
  • degradable active ingredients can be found, for example, in the group of phenoxyacetic acids, ureas, thioureas, thiocarbamates, sulfamides and halogen aromatics.
  • Preferred biocides are:
  • the long-term effect of the biocides is preferably enhanced by microencapsulation.
  • the materials known for this purpose in particular polymers, are suitable.
  • Suitable polymers are, for example, polyesters, natural and synthetic polyamides, melamine resins, polyurethanes, polyureas, polysiloxanes, poly (meth) acrylates and copolymers of (meth) acrylic acid and (meth) acrylic acid esters.
  • crosslinked polymers are particularly suitable as a natural polyamide. This is used in particular as a coacervate and complex coacervate. Under gelatin-containing Kompexkoacervaten in the sense of the invention above all
  • Suitable synthetic polyelectrolytes are copolymers with built-in units of e.g. Maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide.
  • Capsules containing gelatin can be coated with conventional hardening agents such as e.g. Formaldehyde or glutardialdehyde can be crosslinked.
  • the microencapsulated biocide can be present in such a way that a single biocide particle is enclosed by a polymer shell. However, there can also be a polymer particle in which a multiplicity of biocide particles are enclosed or the biocide is present in molecular dispersion.
  • the microencapsulation of isolated biocide particles can be carried out by known methods, for example by
  • polymer particles which contain a large number of biocide particles
  • the production of polymer particles can be carried out, for example, by melt compounding and subsequent comminution.
  • Another well-suited process for producing biocide-containing polymer particles is bead polymerization. In this process, liquid mixtures of monomers and biocide are broken up into small droplets and cured, giving spherical particles in which the active ingredient is enclosed.
  • the following monofunctional monomers and multifunctional monomers, which generally act as crosslinkers, are suitable for producing biocide-containing bead polymers: styrene, vinyl toluene, chlorostyrene, chloromethylstyrene, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, acrylamide, meth- acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, divinylbenzene, diethylene glycol divinyl ether, octadiene-1,7, hexadiene-1,5, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethachrylate and allyl methacrylate.
  • antifouling coatings with active ingredient-containing pearl polymers allow high filling levels and have very good processing properties.
  • the average particle size of the microencapsulated biocides is 0.1 to 200 ⁇ m, preferably 0.2 to 20 ⁇ m.
  • the proportion of the optionally microencapsulated biocides is 1 to 50, preferably 2 to 40% by weight, based on the antifouling coating.
  • At least one organopolysiloxane such as silicone resins, silicone rubber systems, organo-modified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and organosilicone copolymers are used as binders for the antifouling coating according to the invention.
  • organopolysiloxane such as silicone resins, silicone rubber systems, organo-modified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and organosilicone copolymers are used as binders for the antifouling coating according to the invention.
  • organopolysiloxane such as silicone resins, silicone rubber systems, organo-modified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and organosilicone copolymers are used as binders for the antifouling coating according to the invention.
  • the silicone resins used are high molecular weight, physically drying silicone resins of the general formula (1)
  • R 1 for a monovalent hydrocarbon radical with 1-14 C atoms which may have substituents which are inert to water
  • R 2 stands for a monovalent hydrocarbon radical with 1 - 5 carbon atoms
  • Low molecular weight alkoxy-functional silicone resins of the general formula (2) are also used.
  • R 3 for a monovalent hydrocarbon radical having 1-14 carbon atoms can have the substituents which are inert to water
  • R 4 represents a monovalent hydrocarbon radical with 1-5 carbon atoms
  • b means 0, 1, 2, 3, on average 0.2 - 2.0
  • silicone rubber systems All condensation-crosslinking or addition-crosslinking systems known in the prior art, such as room temperature-crosslinking one- or two-component rubbers or vulcanizable two-component liquid rubber, are used as silicone rubber systems.
  • the composition of the silicone rubbers which can be used according to the invention is described, for example, in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, 306 ff.
  • Organomodified polysiloxanes can be linear or branched polysiloxanes, it being possible for the or the organofunctional radicals to be arranged terminally and / or laterally.
  • the binders are generally processed from organic solvents or as an aqueous dispersion.
  • Suitable organic solvents are e.g. aliphatic hydrocarbons, especially gasoline fractions, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters and ethers.
  • the antifouling coating compositions according to the invention may contain conventional ones Auxiliaries such as fillers, solvents, plasticizers, dyes, pigments, catalysts, inhibitors, adhesives, paint additives and / or common dispersing or formulation aids.
  • heavy metal-containing biocides such as N- (cyclo-hexyldiazeniumdioxy) -tributyltin or K-salts, bis-N- (cyclohexyldiazeniumdioxy) - copper;
  • Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate, metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate, oxyfluorosilicate Tributyltin oxide, Cu 2 O, CuO, ZnO; Ag, Zn or Cu-containing zeolites can be contained alone or included in polymeric active ingredients, although the ecological advantage is limited.
  • the mixture was shaken for 20 h, during which the diuron particles were ground to a size of 0.5 to 1.0 ⁇ m.
  • the mixture was then acidified with 15 ml of 1N HCl, heated to 60 ° C. for 1 h, the solid was filtered off, washed with 30 ml of water and dried at 60 ° C. in vacuo. 14.2 g of microencapsulated diuron were obtained.
  • Example 1 was repeated, using Alsystin instead of diuron. 13.5 g of microencapsulated Alsystin were obtained.
  • Example 4 The same procedure as in Example 4. However, a dispersion of 50% by weight Alsystin was incorporated in Isopar G.
  • Example 7 Using a doctor blade with a wet film thickness of 250 ⁇ m applied to an epoxy coated metal plate. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 ⁇ m was obtained.
  • Example 7 Using a doctor blade with a wet film thickness of 250 ⁇ m applied to an epoxy coated metal plate. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 ⁇ m was obtained.
  • Solution 1 g of the microencapsulated diuron in Example 1 was dispersed using a high-speed stirrer. The dispersion was applied with the aid of a doctor blade with a wet film thickness of 250 ⁇ m to a metal plate coated with epoxy paint. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 ⁇ m was obtained.
  • Example 7 The same procedure as in Example 7. However, 1 g of the Alsystin microencapsulated in Example 3 was dispersed in the dilute silicone resin solution.
  • Example 7 The same procedure as Example 7. However, a mixture consisting of 0.5 g of the microencapsulated diuron in Example 1 and 0.5 g of the microencapsulated Alsystin in Example 3 was dispersed in the dilute silicone resin solution.
  • Epoxy paint coated metal plate applied. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 ⁇ m was obtained.
  • Example 2 The same procedure as in Example 11. However, 6.0 g of the microencapsulated diuron in Example 2 were used as the biocide.
  • Example 11 The same procedure as in Example 11. However, 6.0 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
  • Example 16 The same procedure as in Example 11. However, no biocide was used. Example 16
  • 3 g of diuron were dispersed in 27 g of a linear, ⁇ -dihydroxypolydimethylsiloxane with a viscosity of approx. 500 mPas using a high-speed stirrer.
  • the dispersion was mixed with 0.81 crosslinker C5 (available from Bayer AG) and applied with the aid of a doctor blade with a wet film thickness of 250 ⁇ m to an epoxy lacquered metal plate.
  • the coating was dried at room temperature. A homogeneous coating with a layer thickness of approximately 250 ⁇ m was obtained.
  • Example 16 The same procedure as in Example 16. However, 3 g of the microencapsulated diuron in Example 2 were used as the biocide.
  • Example 3 microencapsulated Alsystins used.
  • Example 21 The same procedure as in Example 16. However, no biocide was used. Example 21
  • Example 21 The same procedure as in Example 21. However, 3 g of the microencapsulated diuron in Example 2 were used as the biocide.
  • Example 21 The same procedure as in Example 21. However, 3 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
  • Example 26 The same procedure as in Example 21. However, no biocide was used. Example 26
  • Example 26 The same procedure as in Example 26. However, 2 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
  • Test organism Diatom Nitzschia (benthic diatom) Medium: ASW medium Culture vessels: Erlenmeyer culture flasks Test conditions: Temperature: 18 ° C, artificial continuous light, permanent movement on a tumbler, without additional ventilation.
  • the coating according to the invention from Example 4 contained an organopolysiloxane as a binder and diuron as a degradable biocide. After 14 days of exposure of this coating to benthic diatoms at 18 ° C, artificial continuous light, permanent movement and without additional ventilation, there was only a very small one
  • the coating according to the invention from example 5 likewise showed only very slight fouling (+) in example 30. It contained an organopolysiloxane as binder and alystin as degradable biocide.
  • the coating according to the invention from Example 9 showed no fouling (-) under the test conditions indicated. It also contained an organopolysiloxane as a binder and a mixture of microencapsulated diuron and microencapsulated alystin as degradable biocides. This is surprising in that the biocides were microencapsulated for good long-term effects.
  • the coating from comparative example 10 was biocide-free.
  • the binder was an organopolysiloxane.
  • this coating showed low growth (++).
  • a metal plate coated with an epoxy varnish shows in Example 33 a uniformly good growth (+++).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Biodiversity & Conservation Biology (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the means for producing antifouling paints containing organopolysiloxane as binder and heavy-metal-free microencapsulated biocides as active substances.

Description

AntifoulingbeschichtungAntifouling coating
Die Erfindung betrifft Mittel zur Herstellung von Antifoulingbeschichtungen, die Organopolysiloxane als Bindemittel und Biozide als Wirkstoff enthalten.The invention relates to agents for the production of antifouling coatings which contain organopolysiloxanes as binders and biocides as active ingredients.
Die Antifoulingbeschichtungen dienen zum Schutz von Gegenständen vor Bewuchs, insbesondere von Schiffskörpern, Sieben, Netzen, Bauwerken, Kaianlagen, Signalanlagen und Gegenständen, welche mit See- oder Brackwasser in Verbindung kommen.The anti-fouling coatings are used to protect objects from fouling, in particular ship hulls, sieves, nets, structures, quay systems, signaling systems and objects that come into contact with sea or brackish water.
Die Bewuchsbildung stellt insbesondere bei Schiffen ein großes Problem dar, da z.B. der Reibungswiderstand erhöht wird und infolge des gesteigerten Energieverbrauchs und häufigen Trockendockaufenthalten die Betriebskosten deutlich gesteigert werden. Aus diesem Grund werden Antifoulingbeschichtungen zur Verhinderung von Bewüchsen durch Algen, Seepocken, Röhrenwürmern, Muscheln oder anderen Meeresorganismen seit langem angewendet.The formation of vegetation is a major problem, especially for ships, because e.g. the frictional resistance is increased and the operating costs are significantly increased due to the increased energy consumption and frequent dry dock stays. For this reason, antifouling coatings have been used for a long time to prevent vegetation from algae, barnacles, tube worms, mussels or other marine organisms.
Dabei kann man prinzipiell zwischen biozidhaltigen und biozidfreien Antifoulingbeschichtungen unterscheiden.In principle, a distinction can be made between biocide-containing and biocide-free antifouling coatings.
Biozidfreie Antifoulingbeschichtungen besitzen Antihafteigenschaften, d.h., das Festsetzen von Meeresorganismen soll physikalisch verhindert werden. In der US- A 5 298 060 wird z.B. ein System auf Basis von Organosiliconflüssigkeiten inBiocide-free antifouling coatings have non-stick properties, i.e. the establishment of marine organisms should be physically prevented. For example, in US-A 5 298 060 a system based on organosilicon liquids in
Kombination mit Organosiliconpolymeren beschrieben. Die Wirksamkeit der biozidfreien Antifoulingbeschichtungen ist jedoch begrenzt, so daß dennoch eine mechanische Reinigung des Schiffsrumpfes oder der Unterwasserkonstruktion in relativ kurzen Zeiträumen notwendig wird.Combination with organosilicone polymers described. However, the effectiveness of the biocide-free antifouling coatings is limited, so that mechanical cleaning of the ship's hull or the underwater construction is still necessary in relatively short periods of time.
Des weiteren sind Antifoulingbeschichtung die Biozide enthalten bekannt (US-AAntifouling coatings containing biocides are also known (US-A
4 769 398). Durch die Biozide werden die bewuchsbildenden Organismen abgetötet. Übliche Antifoulingbiozide sind organische Zinnverbindungen oder auch Kupfer- Antimon und Wismutverbindungen. Der Nachteil dieser Biozide ist ihre geringe Umweltvertäglichkeit. Besonders problematisch sind schwermetallhalige Antifoulingbiozide, da diese eine Kontamination des Seewassers und des4,769,398). The biocides kill the growth-forming organisms. Common antifouling biocides are organic tin compounds or copper antimony and bismuth compounds. The disadvantage of these biocides is their low environmental impact. Heavy metal-containing antifouling biocides are particularly problematic since they contaminate the seawater and the
Seebodens, insbesondere im Bereich von Häfen verursachen. Die in der US-A 4 769 398 auch erwähnten rein organischen Biozide weisen dagegen keine gute Langzeitwirkung auf, da der Wirkstoff offensichtlich bereits in der Beschichtung vorzeitig abgebaut wird.Cause seabed, especially in the area of ports. In contrast, the purely organic biocides also mentioned in US Pat. No. 4,769,398 do not have any good ones Long-term effect, since the active ingredient is obviously degraded prematurely in the coating.
Die Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung einer hochwirksamen Antifoulingbeschichtung mit guter Langzeitwirkung und verbesser- ter Umweltverträglichkeit.The object of the present invention is therefore to provide a highly effective antifouling coating with a good long-term effect and improved environmental compatibility.
Überraschenderweise wurde nun gefunden, daß Antifoulingbeschichtungen mit schwermetallfreien Bioziden deutlich verbesserte Antifoulingeigenschaften, verbunden mit einer guten Langzeitwirkung und verbesserter Umweltverträglichkeit aufweisen, wenn als Bindemittel in der Antifoulingbeschichtung Organopolysiloxane verwendet werden.Surprisingly, it has now been found that antifouling coatings with heavy metal-free biocides have significantly improved antifouling properties combined with a good long-term effect and improved environmental compatibility if organopolysiloxanes are used as binders in the antifouling coating.
Gegenstand der Erfindung sind somit Mittel enthaltend a) mindestens ein Organopolysiloxan und b) mindestens ein schwermetallfreies Biozid.The invention thus relates to compositions comprising a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.
Die gute Antifoulingwirkung der erfindungsgemäßen Kombination aus schwer- metallfreiem Biozid und Organopolysiloxan als Bindemittel wird bei der erfin- dungsgemäßen Antifoulingbeschichtung offensichtlich durch einen Synergismus aus biologischer Wirkung des Biozids und physikalischer Wirkung des Organo- polysiloxans hervorgerufen.The good antifouling effect of the combination of heavy metal-free biocide and organopolysiloxane as a binder in the antifouling coating according to the invention is evidently caused by a synergism between the biological effect of the biocide and the physical effect of the organopolysiloxane.
Die erfindungsgemäß vorzugsweise eingesetzten Organopolysiloxane wie Siliconharze, Silicon-Kautschuksysteme, organomodifizierte Polysiloxane wie Polyether- siloxane, epoxy- oder aminofunktionelle Siloxane und Siliconacrylate und/oderThe organopolysiloxanes preferably used according to the invention such as silicone resins, silicone rubber systems, organomodified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and / or
Organosilicon Copolymere weisen durch ihre hydrophobe Oberfläche einerseits eine Antihaftwirkung auf. Dies reduziert den Bewuchs von Algen, Seepocken, Röhrenwürmern, Muscheln oder anderen Meeresorganismen an der Oberfläche von Schiffsrümpfen und Unterwasserkonstruktionen. Gleichzeitig bewirkt die erfin- dungsgemäße hydrophobe Polymermatrix, daß die darin enthaltenen schwermetallfreien Biozide eine verbesserte Langzeitwirkung aufweisen. Dies trifft insbesondere für die in der bevorzugten Ausführungsform eingesetzten, im Seewasser abbaubaren Biozide zu.Organosilicone copolymers have a non-stick effect due to their hydrophobic surface. This reduces the growth of algae, barnacles, tube worms, mussels or other marine organisms on the surface of ship hulls and underwater structures. At the same time, the hydrophobic polymer matrix according to the invention has the effect that the heavy metal-free biocides contained therein have an improved long-term effect. This applies in particular to the biocides which are used in the preferred embodiment and are biodegradable in seawater.
In einer besonders bevorzugten Ausführungsform der Erfindung wird die Langzeitwirkung durch eine zusätzliche Mikroverkapslung des schwermetallfreienIn a particularly preferred embodiment of the invention, the long-term effect is achieved by an additional microencapsulation of the heavy metal-free
Biozids noch erhöht. Als Biozide eignen sich vorzugsweise schwermetallfreie Algizide, Fungizide, Insektizide, Molluskizide und Bakterizide wie z.B.Biocides increased. Suitable biocides are preferably heavy metal-free algicides, fungicides, insecticides, molluscicides and bactericides such as
Triazole:Triazoles:
Azaconazole, Bromuconazole, Cyproconazole, Dichlobutrazol, Diniconazole, Hexconazole, Metconazole, Penconazole, Propiconazole, Tebuconazole, Amitrole,Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexconazole, metconazole, penconazole, propiconazole, tebuconazole, amitrole,
Azocyclotin, Epoxyconazole, Bitertanol, Difenoconazole, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imiben- conazole, Isozofos, Myclobutanil, Paclobutrazol, (±)-cis-l-(4-Chlorphenyl)-2-(lH- l ,2,4-triazol- l -yl)-cycloheptanol, Tetraconazole, Triadimefon, Triadimenol, Triapenthenol, Triflumizole, Triticonazole, Uniconazole sowie deren Metallsalze und Säureaddukte.Azocyclotine, epoxyconazole, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, paclobutrazole, (±) -cis-l- (4-chloro , 2,4-triazol-l -yl) -cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts.
Imidazole:Imidazole:
Imazalil, Pefurazoate, Prochloraz, Triflumizole.Imazalil, Pefurazoate, Prochloraz, Triflumizole.
Thiazolcarboxanilide wie 2,,6'-Dibromo-2-methyl-4-trifluoromethoxy-4,-trifluoro- methyl-l,3-thiazole-5-carboxanilide sowie deren Metallsalze und Säureaddukte.Thiazole carboxanilides such as 2 , 6'-dibromo-2-methyl-4-trifluoromethoxy-4 , -trifluoromethyl-l, 3-thiazole-5-carboxanilides and their metal salts and acid adducts.
Succinat-Dehydrogenase Inhibitoren wie:Succinate dehydrogenase inhibitors such as:
Fenfuram, Furcarbanil, Cyclafluramid, Furmecyclox, Seedvax, Metsulfovax, Pyrocarbolid, Oxycarboxin, Shirlan, Mebenil (Mepronil), Benodanil, Flutolanil (Moncut);Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);
Naphthalin-Derivate wie:Naphthalene derivatives such as:
Terbinafine, Naftifine, Butenafine;Terbinafine, naftifine, butenafine;
Sulfenamide wie Dichlofluanid, Tolylfluanid, Folpet, Fluorfolpet; Captan, Captofol;Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;
Benzimidazole wie Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiopho- natmethyl, Thiabendazole oder deren Salze; Morpholinderivate wie Tridemorph, Fenpropimorph, Falimorph, Dimethomorph, Dodemorph; AI dimorph, Fenpropidin und ihre arylsulfonsauren Salze, wie z.B. p- Toluolsulfonsäure und p-Dodecylphenyl-sulfonsäure;Benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate methyl, thiabendazole or their salts; Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph; AI dimorphic, fenpropidine and their aryl sulfonic acid salts, such as p-toluenesulfonic acid and p-dodecylphenyl sulfonic acid;
Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram:Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam, Metiram, Thiram Zeneb, Ziram:
Benzthiazole wie 2-Mercaptobenzothiazol;Benzothiazoles such as 2-mercaptobenzothiazole;
Benzamide wie 2,6-Dichloro-N-(4-trifluoromethylbenzyl)-benzamide;Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;
Borverbindungen wie Borsäure, Borsäureester, Borax;Boron compounds such as boric acid, boric acid ester, borax;
Formaldehyd und Formaldehydabspaltende Verbindungen wie Benzylalkoholmono- (poiy)-hemiformal, Oxazolidine, Hexa-hydro-S-triazine, N-Methylolchloracetamid,Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poiy) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide,
Paraformadehyd, Nitropyrin, Oxolinsäure, Tecloftalam;Paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;
Tris-N-(cyclohexyldiazeniumdioxy)-aluminium;Tris-N- (cyclohexyldiazeniumdioxy) aluminum;
N-Methylisothiazolin-3-on, 5-Chlor-N-methylisothiazolin-3-on, 4,5-Dichloro-N- octylisothiazolin-3-on, N-Octyl-isothiazolin-3-on, 4,5-Trimethylen-isothiazolinone, 4,5-Benzisothiazolinone;N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5-trimethylene isothiazolinone, 4,5-benzisothiazolinone;
Aldehyde wie Zimtaldehyd, Formaldehyd, Glutardialdehyd, ß-Bromzimtaldehyd; Thiocyanate wie Thiocyanatomethylthiobenzothiazol, Methylenbisthiocyanat, usw;Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc;
quartäre Ammoniumverbindungen wie Benzyldimethyltetradecylammoniumchlorid, Benzyldimethyldodecylammoniumchlorid, Didecyldimethylammoniumchlorid;quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
Iodderivate wie Diiodmethyl-p-tolylsulfon, 3-Iod-2-propinyl-alkohol, 4-Chlor- phenyl-3-iodpropargylformal, 3-Brom-2,3-diiod-2-propenylethylcarbamat, 2,3,3-Tri- iodallylalkohol, 3-Brom-2,3-diiod-2-propenylalkohol, 3-Iod-2-propinyl-n-butyl- carbamat, 3-Iod-2-propinyl-n-butylharnstoff, 3-Iod-2-propinyl-n-hexylcarbamat, 3- Iod-2-propinyl-cyclohexylcarbamat, 3-Iod-2-propinyl-phenylcarbamat;Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-tri- iodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-butyl urea, 3-iodo-2-propynyl n-hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 3-iodo-2-propynyl phenyl carbamate;
Phenolderivate wie Tribromphenol, Tetrachlorphenol, 3-Methyl-4-chlorphenol,Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,
3,5-Dimethyl-4-chlorphenol, Phenoxyethanol, Dichlorphen, o-Phenylphenol, m- Phenylphenol, p-Phenylphenol, 2-Benzyl-4-chlorphenol und deren Alkali- und Erdalkalimetallsalze. Mikrobizide mit aktivierter Halogengruppe wie Chloracetamid, N-Methylolchloracetamid, Bronopol, Bronidox, Tectamer wie 2-Brom-2-nitro-l,3-propandiol, 2- Brom-4'-hydroxy-acetophenon, 2,2-Dibrom-3-nitril-propionamid, 1 ,2-Dibrom-2,4- dicyanobutan, ß-Brom-ß-nitrostyrol;3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts. Microbicides with activated halogen group such as chloroacetamide, N-methylolchloroacetamide, Bronopol, Bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3- nitrile propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene;
Pyridine wie l-Hydroxy-2-pyridinthion (und ihre Na-, Fe-, Cu-, Mn-, Zn-Salze),Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Cu, Mn, Zn salts),
Tetrachlor-4-methylsulfonylpyridin, Pyrimethanol, Mepanipyrim, Dipyrithion;Tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;
Dialkyldithiocarbamate wie Na-Salze von Dialkyldithiocarbamaten, Tetramethyl- thiuramdisulfid, Kalium-N-methyl-dithiocarbamat;Dialkyldithiocarbamates such as sodium salts of dialkyldithiocarbamates, tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;
Nitrile wie 2,4,5, 6-Tetrachlorisophthalodinitril, Dinatrium-cyano-dithioimidocarba- mat;Nitriles such as 2,4,5, 6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;
Chinoline wie 8-Hydroxychinolin und deren Cu-Salze;Quinolines such as 8-hydroxyquinoline and their Cu salts;
Mucochlor säure, 5-Hydroxy-2(5H)-furanon;Mucochloric acid, 5-hydroxy-2 (5H) furanon;
4,5-Dichlorodithiazolinon, 4,5-Benzdithiazolinon, 4,5-Trimethylendithiazolinon, 4,5-Dichlor-(3H)-l,2-dithiol-3-on, 3,5-Dimethyl-tetrahydro-l,3,5-thiadiazin-2-thion,4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetrahydro-l, 3, 5-thiadiazin-2-thione,
N-(2-p-Chlorbenzoylethyl)-hexaminiumchlorid, Kalium-N-hydroxy methyl-N'- methyl-dithiocarbamat,N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxy methyl-N'-methyl-dithiocarbamate,
2-Oxo-2-(4-hydroxy-phenyl)acethydroximsäure-chlorid,2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride,
Phenyl-(2-chlor-cyan-vinyl)sulfon,Phenyl- (2-chloro-cyano-vinyl) sulfone,
Phenyl-(l,2-dichlor-2-cyan-vinyl)sulfon;Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;
Desweiteren werden auch gut wirksame Mittel mit den folgenden Wirkstoffen hergestellt:Furthermore, well-effective agents are made with the following active ingredients:
Fungizide:Fungicides:
Methyl-(E)-methoximino[α-(o-tolyloxy)-o-tolyl]acetate, Methyl-(E)-2-{2-[6-(2- cyanphenoxy)-pyrimidin-4-yl-oxy]phenyl}-3-methoxyacrylat, Acypetacs, 2-Aminobutane, Ampropylfos, Anilazine, Benalaxyl, Bupirimate, Chinomethionat, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl,Methyl- (E) -methoximino [α- (o-tolyloxy) -o-tolyl] acetate, methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl,
Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobenfos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide,Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Proponomone, Pyilonium, Propyloxinone, Proamonoxin, Proiloxin, Proamonoxin, Proconoxin, Proiloxin, Proconoxin, Proamon, Pyronoxin, Proconoxin, Proamonoxin Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide,
Trichlamide, Tricyclazole, Triforine, Vinclozolin.Trichlamide, Tricyclazole, Triforine, Vinclozolin.
Insektizide:Insecticides:
Phosphorsäureester wie Azinphos-ethyl, Azinphos-methyl, α-l(4-Chlorphenyl)-4- (O-ethyl, S-propyl)phosphoryloxy-pyrazol, Chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, Diazinon, Dichlorvos, Dimethoate, Ethoate, Ethoprophos,Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, Dimethoate, Ethoate, Ethoprophos,
Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos und Trichlorphon;Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone;
Carbamate wie Aldicarb, Bendiocarb, α-2-(l-Methylpropyl)-phenylmethylcarbamat, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb,Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb,
Isoprocarb, Methomyl, Oxamyl, Pirimicarb, Promecarb, Propoxur und Thiodicarb;Isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
Organosiliciumverbindungen, vorzugsweise Dimethyl(phenyl)silyl-methyl-3- phenoxybenzylether wie Dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxy- benzylether oderOrganosilicon compounds, preferably dimethyl (phenyl) silyl-methyl-3-phenoxybenzyl ether such as dimethyl- (4-ethoxyphenyl) -silylmethyl-3-phenoxy-benzyl ether or
(Dimethylphenyl)-silyl-methyl-2-phenoxy-6-pyridylmethylether wie z.B. Dimethyl-(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl
(9-ethoxy-phenyl)-silylmethyl-2-phenoxy-6-pyridylmethylether oder [(Phenyl)-3-(3- phenoxyphenyl)-propyl](dimethyl)-silane wie z.B. (4-Ethoxyphenyl)-[3-(4-fluoro-3- phenoxyphenyl-propyljdimethyl-silan, Silafluofen;(9-ethoxy-phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) propyl] (dimethyl) silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl-dimethyl-silane, silafluofen;
Pyrethroide wie Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3- phenyl-2-methylbenzyl-2,2-dimethyl-3-(2-chlor-2-trifluor-methylvinyl)cyclopropan- carboxylat, Fenpropathrin, Fenfluthrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate, Permethrin, Resmethrin und Tralomethrin;Pyrethroids such as Allethrin, Alphamethrin, Bioresmethrin, Byfenthrin, Cycloprothrin, Cyfluthrin, Decamethrin, Cyhalothrin, Cypermethrin, Deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trif -methylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin;
Nitroimine und Nitromethylene wie l-[(6-Chlor-3-pyridinyl)-methyl]-4,5-dihydro- N-nitro-lH-imidazol-2-amin (Imidacloprid), N-[(6-Chlor-3-pyridyl)methyl-]N2- cyano-N^methylacetamide (NI-25);Nitroimines and nitromethylenes such as l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (imidacloprid), N - [(6-chloro-3 -pyridyl) methyl-] N 2 - cyano-N ^ methylacetamide (NI-25);
Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethrins, Pyridaben, Pyridafenthion, Pyriproxyfen, Quinalphos, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride,Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethriproxyphid, Pyrethridafid, Pyrethridafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafide, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride,
Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Trifiumuron, Trimethacarb, Vamidothion, Verticillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S)-cyclopentenyl isomer, Bromophos,Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl-phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralometuronamide, Triflomethuron, Triflomethuron, Triflomethuron, Trifomarburide Verticillium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioallethrin (S) -cyclopentenyl isomer, Bromophos,
Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionat, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chlorpyrifos, Cyanophos, Beta-Cyfluthrin, Alpha- cypermethrin, Cyophenothrin, Cyromazine, Dazomet, DDT, Demeton-S- methylsulphon, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb,Bromophos-ethyl, buprofezin, cadusafos, calcium polysulfide, carbophenothione, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha- cypermethrin, cdomomethothrin, cyazometothrin, cyophenothrin - methylsulphone, diafenthiuron, dialifos, dicrotophos, diflubenzuron, dinoseb,
Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalerate, Ethiofencarb, Ethion, Etofenprox, Fenobucarb, Fenoxycarb, Fensulfothion, Fipronil, Flucycloxuron, Flufenprox, Flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos,Deoxabenzofos, Diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil, flucycloxuron, flufenprox, flufenoxuron, fonofos, Formetanate, formothion, Fosmethilan, furathiocarb, heptachlor, hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos,
Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, Chloride, Metam, Metarthizium, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol,Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, Chloride, Metam, Metarthician, anisopliae, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanocinphodol, Neophi, Mocarbophone, Neo, Mocarbophone, Neo, Mocarbox, Neo, Mocarbox, Neo, Mocarbo sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol,
Petroleum oils, Phenothrin, Phenthoate, Phorate;Petroleum oils, phenothrin, phenthoates, phorates;
Molluscicides:Molluscicides:
Fentinacetate, Metaldehyde, Methiocarb. Niclosamide, Thiodicarb, Trimethacarb; Algicide:Fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb; Algicide:
Dichlororphen, Endothal, Fentinacetate, Quinoclamine;Dichlororphes, endothal, fentin acetates, quinoclamines;
Herbicides:Herbicides:
Diuron, Dichlorophen, Endothal, Fentinacet, Quinochlamine.Diuron, dichlorophene, endothal, fentinacet, quinochlamine.
Als Biozide eignen sich vorzugsweise Algizide wie Diuron, Dichlorophen,Preferred biocides are algicides such as diuron, dichlorophene,
Endothal, Fentinacetat, Quinoclamine, Molluscicide wie Fentinacetat, Metaldehyd, Methiocarb, Niclosamid, Thiodicarb und Trimethacarb, Fungizide wie Dichlo- fluanid, Tolylfluanid, Iodpropargylbutylcarbamat, Fluorfolpet und Azole wie Tebu- conazole oder herkömmliche Antifoulingwirkstoffe wie 2-(N,N-Dimethylthiocar- bamoylthio)-5-nitrothiazyl, Tetrabutyldistannoxan, 2-tert.-Butylamino-4-cyclo- propylamino-6-methylthio-l,3,5-triazin, 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-on, 2,4,5,6-Tetrachloroisophthalodinitril, Tetramethylthiuramdisulfid, 2,4,6-Trichlor- phenylmaleinimid, 2,3,5,6-Tetrachlor-4-(methylsulfonyl)-pyridin, Diiodmethyl- paratrylsulfon, Thiabendazol, Tetraphenylboronpyridinsalz, Natriumsalz von 2-Pyridinthiol-l-oxid.Endothal, fentin acetate, quinoclamines, molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb, fungicides such as dichlorofluanide, tolylfluanid, iodopropargylbutylcarbamate, fluorfolpet and azoles such as tebuconazole actives such as tebuconazole actin or antioxidants, bamoylthio) -5-nitrothiazyl, tetrabutyldistannoxane, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-l, 3,5-triazine, 4,5-dichloro-2-n-octyl-4-isothiazoline- 3-one, 2,4,5,6-tetrachloroisophthalodinitrile, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethyl paratryl sulfone, thiabendazole, Tetraphenylboronpyridinsalz, sodium salt of 2-pyridinthiol-l-oxide.
Erfindungsgemaß bevorzugte Biozide sind auch Benzothiophen-2-carboxamid-S,S- dioxide der Formel (I)Biocides preferred according to the invention are also benzothiophene-2-carboxamide-S, S-dioxide of the formula (I)
in welcherin which
R1 für gegebenenfalls substituiertes Alkyl, für Alkenyl oder Alkinyl, für jeweils gegebenenfalls substituiertes Cycloalkyl oder Cycloalkylalkyl, oder für jeweils gegebenenfalls substituiertes Aralkyl, Aralkenyl, Aralkinyl oder Aryl steht,R 1 stands for optionally substituted alkyl, for alkenyl or alkynyl, for each optionally substituted cycloalkyl or cycloalkylalkyl, or for each optionally substituted aralkyl, aralkenyl, aralkynyl or aryl,
R für Wasserstoff oder für gegebenenfalls substituiertes Alkyl steht oder R1 und R2 gemeinsam mit dem Stickstoffatom an welches sie gebunden sind für einen gegebenenfalls substituierten Heterocyclus stehen undR represents hydrogen or optionally substituted alkyl or R 1 and R 2 together with the nitrogen atom to which they are attached represent an optionally substituted heterocycle and
R3, R4, R5 und R6 unabhängig voneinander jeweils für Wasserstoff, Halogen, Cyano, Nitro, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy oder Halogenalkylthio stehen.R 3 , R 4 , R 5 and R 6 each independently represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio.
Insbesondere bevorzugt ist die Verbindung N-Cyclohexylbenzothiophen-2-carb- oxamid-S,S-dioxid.The compound N-cyclohexylbenzothiophene-2-carboxamide-S, S-dioxide is particularly preferred.
Besonders gute Wirkungen werden auch mit Wirkstoffkombinationen vozugsweise der genannten Biozide erzielt.Particularly good effects are also achieved with combinations of active substances, preferably the biocides mentioned.
Besonders bevorzugt sind diejenigen Biozide die abbaubar sind.Those biocides that are degradable are particularly preferred.
Unter abbaubar im Sinne der Erfindung werden solche Biozide verstanden, die im Meerwasser bei 25°C eine Halbwertszeit von weniger 180 Tagen, vorzugsweise weniger als 90 Tagen aufweisen. Der Mechanismus der Abbaureaktion ist für den erfinderischen Effekt nicht entscheidend. Es kann ein chemischer Abbau durch z.B. Hydrolyse oder Oxidation, ein photochemischer Abbau oder ein biologischer Abbau durch Microorganismen sein.Degradable in the sense of the invention is understood to mean those biocides which have a half-life of less than 180 days, preferably less than 90 days, in sea water at 25 ° C. The mechanism of the degradation reaction is not critical to the inventive effect. Chemical degradation by e.g. Hydrolysis or oxidation, photochemical degradation or biodegradation by microorganisms.
Beispiele für geeignete abbaubare Wirkstoffe finden sich beispielsweise in der Gruppe der Phenoxiessigsäuren, Harnstoffe, Thioharn Stoffe, Thiocarbamate, Sulfamide und Halogenaromaten.Examples of suitable degradable active ingredients can be found, for example, in the group of phenoxyacetic acids, ureas, thioureas, thiocarbamates, sulfamides and halogen aromatics.
Bevorzugte Biozide sind:Preferred biocides are:
Die Langzeitwirkung der Biozide wird vorzugsweise noch durch eine Mikroverkapselung verstärkt. Dabei kommen für die Mikroverkapselung der Biozide kommen die für diesen Einsatzzweck bekannten Materialien, insbesondere Polymere in Frage. Geeignete Polymere sind beispielsweise Polyester, natürliche und synthetische Polyamide, Melaminharze, Polyurethane, Polyharnstoffe, Poly- siloxane, Poly(meth)acrylate sowie Copolymerisate aus (Meth)acrylsäure und (Meth)acrylsäureester. In vielen Fällen ist es vorteilhaft vernetzte Polymere anzuwenden. Als natürliches Polyamid ist Gelatine besonders gut geeignet. Diese kommt insbesondere als Koazervat und Komplexkoazervat zur Anwendung. Unter gelatinehaltigen Kompexkoazervaten im Sinne der Erfindung werden vor allem The long-term effect of the biocides is preferably enhanced by microencapsulation. For the microencapsulation of the biocides, the materials known for this purpose, in particular polymers, are suitable. Suitable polymers are, for example, polyesters, natural and synthetic polyamides, melamine resins, polyurethanes, polyureas, polysiloxanes, poly (meth) acrylates and copolymers of (meth) acrylic acid and (meth) acrylic acid esters. In many cases it is advantageous to use crosslinked polymers. Gelatin is particularly suitable as a natural polyamide. This is used in particular as a coacervate and complex coacervate. Under gelatin-containing Kompexkoacervaten in the sense of the invention above all
Kombinationen von Gelatine und synthetischen Polyelektrolyten verstanden. Geeignete synthetische Polyelektrolyte sind Copolymerisate mit eingebauten Einheiten von z.B. Maleinsäure, Acrylsäure, Methacrylsäure, Acrylamid und Methacrylamid. Gelatinehaltige Kapseln können mit üblichen Härtungsmitteln wie z.B. Formaldehyd oder Glutardialdehyd vernetzt werden.Combinations of gelatin and synthetic polyelectrolytes understood. Suitable synthetic polyelectrolytes are copolymers with built-in units of e.g. Maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide. Capsules containing gelatin can be coated with conventional hardening agents such as e.g. Formaldehyde or glutardialdehyde can be crosslinked.
Das mikroverkapselte Biozid kann in der Weise vorliegen, daß ein einzelnes Biozidteilchen von einer Polymerhülle umschlossen wird. Es kann aber auch ein Polymerpartikel vorliegen, in dem eine Vielzahl von Biozidteilchen eingeschlossen sind oder das Biozid molekulardispers vorliegt. Die Mikroverkapselung isolierter Biozidteilchen kann durch bekannte Methoden erfolgen zum Beispiel durchThe microencapsulated biocide can be present in such a way that a single biocide particle is enclosed by a polymer shell. However, there can also be a polymer particle in which a multiplicity of biocide particles are enclosed or the biocide is present in molecular dispersion. The microencapsulation of isolated biocide particles can be carried out by known methods, for example by
Aufbringen eines fertigen Polymeren aus Lösung durch Ausfällen des Polymers oder Verdampfen des Lösungsmittels. Es ist auch möglich das Polymer durch Aufbaureaktionen, wie Polymerisation, Polyaddition oder Polykondensation auf der Oberfläche des Biozidteilchens zu erzeugen.Application of a finished polymer from solution by precipitation of the polymer or evaporation of the solvent. It is also possible to produce the polymer on the surface of the biocide particle by means of build-up reactions, such as polymerization, polyaddition or polycondensation.
Die Herstellung von Polymerpartikel, die eine Vielzahl von Biozidteilchen eingeschlossen enthalten, kann z.B. durch Schmelzencompoundierung und anschließende Zerkleinerung erfolgen. Ein weiteres gut geeignetes Verfahren zur Herstellung von biozidhaltigen Polymerpartikeln ist die Perlpolymerisation. Bei diesem Verfahren werden flüssige Mischungen aus Monomeren und Biozid zu kleinen Tröpfchen zerteilt und ausgehärtet, wobei kugelförmige Partikel erhalten werden, in denen der Wirkstoff eingeschlossen ist. Zur Herstellung biozidhaltiger Perl- polymerisate sind beispielsweise die folgenden monofunktionellen Monomere und multifunktionellen Monomere, die in der Regel als Vernetzer wirken, geeignet: Styrol, Vinyltoluol, Chlorstyrol, Chlormethylstyrol, Acrylsäure, Methacrylsäure, Acrylsäurester, Methacrylsäureester, Acrylnitril, Methacrylnitil, Acrylamid, Meth- acrylamid, Vinylchlorid, Vinylidenchlorid, Vinylacetat, Divinylbenzol, Diethylen- glycoldivinylether, Octadien-1,7, Hexadien-1,5, Ethylenglycoldimethacrylat, Tri- ethylenglycoldimethacrylat, Trimethylolpropan-trimethachrylat und Allylmeth- acrylat.The production of polymer particles, which contain a large number of biocide particles, can be carried out, for example, by melt compounding and subsequent comminution. Another well-suited process for producing biocide-containing polymer particles is bead polymerization. In this process, liquid mixtures of monomers and biocide are broken up into small droplets and cured, giving spherical particles in which the active ingredient is enclosed. The following monofunctional monomers and multifunctional monomers, which generally act as crosslinkers, are suitable for producing biocide-containing bead polymers: styrene, vinyl toluene, chlorostyrene, chloromethylstyrene, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, acrylamide, meth- acrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, divinylbenzene, diethylene glycol divinyl ether, octadiene-1,7, hexadiene-1,5, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethachrylate and allyl methacrylate.
Es wurde gefunden, daß Antifoulingbeschichtungen mit wirkstoffhaltigen Perlpoly- merisaten hohe Füllgrade erlauben und sehr gute Verarbeitungseigenschaften aufweisen.It has been found that antifouling coatings with active ingredient-containing pearl polymers allow high filling levels and have very good processing properties.
Die mittlere Teilchengröße der mikroverkapselten Biozide beträgt 0.1 bis 200 μm, vorzugsweise 0.2 bis 20 μm.The average particle size of the microencapsulated biocides is 0.1 to 200 μm, preferably 0.2 to 20 μm.
Der Anteil der gegebenenfalls mikroverkapselten Biozide beträgt 1 bis 50, vorzugsweise 2 bis 40 Gew.-%, bezogen auf die Antifoulingbeschichtung.The proportion of the optionally microencapsulated biocides is 1 to 50, preferably 2 to 40% by weight, based on the antifouling coating.
Als Bindemittel für die erfindungsgemäße Antifoulingbeschichtung werden mindestens ein Organopolysiloxan wie Siliconharze, Silicon-Kautschuksysteme, organo- modifizierte Polysiloxane wie Polyethersiloxane, epoxy- oder aminofunktionelle Siloxane und Siliconacrylate sowie Organosilicon Copolymere eingesetzt. Es können jedoch auch Mischungen der genannten Polysiloxane eingesetzt werden.At least one organopolysiloxane such as silicone resins, silicone rubber systems, organo-modified polysiloxanes such as polyether siloxanes, epoxy- or amino-functional siloxanes and silicone acrylates and organosilicone copolymers are used as binders for the antifouling coating according to the invention. However, mixtures of the polysiloxanes mentioned can also be used.
Als Siliconharze werden hochmolekulare, physikalisch trocknende Siliconharze der allgemeinen Formel (1)The silicone resins used are high molecular weight, physically drying silicone resins of the general formula (1)
(1) Ri(R2Q)bsi(0)(4.(a+b)) , (1) Ri (R 2Q ) b si (0) (4. (A + b)),
2 wobei2 where
R1 für einen einwertigen Kohlenwasserstoffrest mit 1 - 14 C- Atomen der gegen Wasser inerte Substituenten aufweisen kannR 1 for a monovalent hydrocarbon radical with 1-14 C atoms which may have substituents which are inert to water
R2 für einen einwertigen Kohlenwasserstoffrest mit 1 - 5 C-Atomen stehtR 2 stands for a monovalent hydrocarbon radical with 1 - 5 carbon atoms
a 0, 1, 2 oder 3, durchschnittlich 0,75 - 1,5, unda 0, 1, 2 or 3, average 0.75 - 1.5, and
b 0, 1, 2, 3, durchschnittlich 0,01 - 0,1 bedeutetb means 0, 1, 2, 3, on average 0.01 - 0.1
eingesetzt. Ebenfalls eingesetzt werden niedernolekulare alkoxyfunktionelle Siliconharze der allgemeinen Formel (2)used. Low molecular weight alkoxy-functional silicone resins of the general formula (2) are also used.
(2) R x (R < Q ) y S i(Q ) (4_(x+y)) _(2) R x (R <Q) y S i (Q) (4 _ (x + y)) _
wobei R3 für einen einwertigen Kohlenwasserstoffrest mit 1 - 14 C- Atomen der gegen Wasser inerte Substituenten aufweisen kannwhere R 3 for a monovalent hydrocarbon radical having 1-14 carbon atoms can have the substituents which are inert to water
R4 für einen einwertigen Kohlenwasserstoffrest mit 1 - 5 C-Atomen stehtR 4 represents a monovalent hydrocarbon radical with 1-5 carbon atoms
x 0, 1, 2 oder 3, durchschnittlich 0,75 - 1,5, undx 0, 1, 2 or 3, average 0.75 - 1.5, and
b 0, 1, 2, 3, durchschnittlich 0,2 - 2,0 bedeutetb means 0, 1, 2, 3, on average 0.2 - 2.0
sowie Mischungen aus hochmolekularen Siliconharzen und niedermolekularen alkoxyfunktionellen Siliconharzen.as well as mixtures of high molecular weight silicone resins and low molecular weight alkoxy-functional silicone resins.
Als Silicon-Kautschuksysteme werden alle nach dem Stand der Technik bekannten kondensationsvernetzenden oder additionsvernetzenden Systeme wie raumtemperaturvernetzende Ein- oder Zweikomponentenkautschuke oder vulkanisierbarer Zweikomponentenflüssigkautschuk verwendet. Die Zusammensetzung der erfindungsgemäß einsetzbaren Silicon-Kautschuke wird beispielsweise beschrieben in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, 306 ff.All condensation-crosslinking or addition-crosslinking systems known in the prior art, such as room temperature-crosslinking one- or two-component rubbers or vulcanizable two-component liquid rubber, are used as silicone rubber systems. The composition of the silicone rubbers which can be used according to the invention is described, for example, in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A23, 306 ff.
Organomodifizierte Polysiloxane können lineare oder verzweigte Polysiloxane sein, wobei der oder die organofunktionellen Reste endständig und/oder seiten- ständig angeordnet sein können.Organomodified polysiloxanes can be linear or branched polysiloxanes, it being possible for the or the organofunctional radicals to be arranged terminally and / or laterally.
Die Bindemittel werden im allgemeinen aus organischen Lösungsmitteln oder als wäßrige Dispersion verarbeitet. Geeignete organische Lösungsmittel sind z.B. aliphatische Kohlenwasserstoffe, insbesondere Benzinfraktionen, aromatische Kohlenwasserstoffe, Halogenkohlenwasserstoffe, Alkohole, Ketone, Ester und Ether.The binders are generally processed from organic solvents or as an aqueous dispersion. Suitable organic solvents are e.g. aliphatic hydrocarbons, especially gasoline fractions, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters and ethers.
Die erfindungsgemäßen Antifoulingbeschichtungsmittel enthalten neben den schwermetallfreien Bioziden und den Organopolysiloxanen gegebenenfalls übliche Hilfsmittel wie z.B. Füllstoffe, Lösungsmittel, Weichmacher, Farbstoffe, Pigmente, Katalysatoren, Inhibitoren, Haftmittel, Lackadditive und/oder gängige Dispergier- bzw. Formulierhilfsmittel. Selbstverständlich können neben den schwermetallfreien Bioziden auch noch schwermetallhaltige Biozide wie z.B. N-(Cyclo-hexyl- diazeniumdioxy)-tributylzinn bzw. K-Salze, Bis-N-(cyclohexyldiazeniumdioxy)- kupfer; Metallseifen wie Zinn-, Kupfer-, Zinknaphtenat, -octoat, 2-ethylhexanoat, -oleat, -phosphat, -benzoat, Metallsalze wie Kupferhydroxycarbonat, Natrium- dichromat, Kaliumdichromat, Kaliumchromat, Kupfersulfat, Kupferchlorid, Kupferborat, Zinkfluorosilikat, Kupferfluorosilikat, Oxide wie Tributylzinnoxid, Cu2O, CuO, ZnO; Ag, Zn oder Cu-haltige Zeolithe allein oder eingeschlossen in polymere Wirkstoffe enthalten sein, wobei allerdings der ökologische Vorteil eingeschränkt wird.In addition to the heavy metal-free biocides and the organopolysiloxanes, the antifouling coating compositions according to the invention may contain conventional ones Auxiliaries such as fillers, solvents, plasticizers, dyes, pigments, catalysts, inhibitors, adhesives, paint additives and / or common dispersing or formulation aids. Of course, in addition to the heavy metal-free biocides, heavy metal-containing biocides such as N- (cyclo-hexyldiazeniumdioxy) -tributyltin or K-salts, bis-N- (cyclohexyldiazeniumdioxy) - copper; Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate, metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate, oxyfluorosilicate Tributyltin oxide, Cu 2 O, CuO, ZnO; Ag, Zn or Cu-containing zeolites can be contained alone or included in polymeric active ingredients, although the ecological advantage is limited.
Durch die folgenden Beispiele soll die Erfindung näher erläutert werden. Die Erfindung ist jedoch nicht auf die Beispiele beschränkt. The invention is illustrated by the following examples. However, the invention is not limited to the examples.
Beispiele:Examples:
Beispiel 1example 1
Mikroverkapslung von Diuron (Umhüllung)Diuron Microencapsulation (Envelope)
In einer Perlmühle wurdenIn a pearl mill
12 g Diuron,12 g diuron,
0,06 g Dispergiermittel (Baykanol SI, Bayer AG),0.06 g dispersant (Baykanol SI, Bayer AG),
48 g einer 5 %igen, wäßrigen alkalischen Lösung eines Terpolymerisates aus 24 Gew.-% Methacrylsäure, 36 Gew.-% Methacrylat und 40 Gew.-% Butylacrylat und 10 g Wasser48 g of a 5% aqueous alkaline solution of a terpolymer made of 24% by weight methacrylic acid, 36% by weight methacrylate and 40% by weight butyl acrylate and 10 g water
eingewogen. Die Mischung wurde 20 h geschüttelt, wobei die Diuronpartikel auf eine Größe von 0,5 bis 1,0 μm zerkleinert wurden. Anschließend wurde mit 15 ml ln-HCl angesäuert, 1 h auf 60°C erhitzt, der Feststoff abfiltriert, mit 30 ml Wasser gewaschen und bei 60°C im Vakuum getrocknet. Man erhielt 14,2 g mikrover- kapseltes Diuron.weighed in. The mixture was shaken for 20 h, during which the diuron particles were ground to a size of 0.5 to 1.0 μm. The mixture was then acidified with 15 ml of 1N HCl, heated to 60 ° C. for 1 h, the solid was filtered off, washed with 30 ml of water and dried at 60 ° C. in vacuo. 14.2 g of microencapsulated diuron were obtained.
Beispiel 2Example 2
Mikroverkapselung von Diuron (Perlpolymerisation)Microencapsulation of diuron (bead polymerization)
In einer Kugelmühle wurden 100 g Diuron, 30 g hochdisperse Kieselsäure (HDK H 2000), Wacker Chemie GmbH), 285 g Methylmethacrylat und 15 g Ethylenglycoldimethacrylat 10 h bei Raumtemperatur intensiv durchmischt. Anschließend wurden 3 g Dibenzoylperoxid zugesetzt und die erhaltene Mischung in einen 31-Rührreaktor der 1,5 1 einer 1 %igen wäßrigen alkalischen Lösung (mit NaOH auf pH 0,8 eingestellt) eines Copolymerisates aus 50 Gew.-% Methacrylsäure und 50 Gew.-% Methylmethacrylat enthielt, überführt. Die Rührge- schwindigkeit wurde auf 600 rpm eingestellt und die Temperatur 2 h bei 78°C und dann 1 h bei 85°C gehalten. Nach dem Abkühlen wurde der erhaltene Feststoff durch Dekantieren isoliert, mehrfach mit Wasser gewaschen und bei 80°C 12 h lang getrocknet. Man erhielt 385 g mikroverkapseltes Diuron in Form von Perl- polymerisaten mit einer mittleren Teilchengröße von 15 μm. Beispiel 3100 g of diuron, 30 g of highly disperse silica (HDK H 2000), Wacker Chemie GmbH), 285 g of methyl methacrylate and 15 g of ethylene glycol dimethacrylate were mixed thoroughly for 10 hours at room temperature in a ball mill. Then 3 g of dibenzoyl peroxide were added and the mixture obtained in a 31 stirred reactor containing 1.5 l of a 1% strength aqueous alkaline solution (adjusted to pH 0.8 with NaOH) of a copolymer of 50% by weight methacrylic acid and 50% by weight. -% contained methyl methacrylate, transferred. The stirring speed was set to 600 rpm and the temperature was kept at 78 ° C. for 2 hours and then at 85 ° C. for 1 hour. After cooling, the solid obtained was isolated by decanting, washed several times with water and dried at 80 ° C. for 12 hours. 385 g of microencapsulated diuron were obtained in the form of bead polymers with an average particle size of 15 μm. Example 3
Mikroverkapselung von Alsystin (Umhüllung)Alsystin microencapsulation (encapsulation)
Beispiel 1 wurde wiederholt, wobei anstelle von Diuron Alsystin eingesetzt wurde. Man erhielt 13,5 g mikroverkapseltes Alsystin.Example 1 was repeated, using Alsystin instead of diuron. 13.5 g of microencapsulated Alsystin were obtained.
Beispiel 4Example 4
Erfindungsgemäße BeschichtungCoating according to the invention
2 g einer Dispersion, bestehend aus 50 Gew.-% Diuron und 50 Gew.-% Isopar G wurden in 11,67 g einer Siliconharzlösung mit einer Viskosität von 3 000 mPas, bestehend aus 77,1 Gew.-% eines hochmolekularen, physikalisch trocknenden Organopolysiloxans und 22,9 Gew.-% Isopar G mit Hilfe eines Schnellrührers dispergiert. Die Dispersion wurde mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde 10 h bei 60°C getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 150 μm.2 g of a dispersion consisting of 50% by weight of diuron and 50% by weight of Isopar G were physically dissolved in 11.67 g of a silicone resin solution with a viscosity of 3,000 mPas, consisting of 77.1% by weight of a high molecular weight dispersing drying organopolysiloxane and 22.9 wt .-% Isopar G using a high-speed stirrer. The dispersion was applied with the aid of a doctor blade with a wet film thickness of 250 μm to a metal plate coated with epoxy paint. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 μm was obtained.
Beispiel 5Example 5
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 4. Es wurde jedoch eine Dispersion aus 50 Gew.-% Alsystin in Isopar G eingearbeitet.The same procedure as in Example 4. However, a dispersion of 50% by weight Alsystin was incorporated in Isopar G.
Beispiel 6 Erfindungsgemäße BeschichtungExample 6 Coating According to the Invention
3 g einer Dispersion, bestehend aus 33 Gew.-% des in Beispiel 2 mikroverkapselten Diurons und 77 Gew.-% Isopar G wurden in 11,67 g einer Siliconharzlösung mit einer Viskosität von 3 000 mPas, bestehend aus 77,1 Gew.-% eines hochmolekularen, physikalisch trocknenden Organopolysiloxans und 22,9 Gew.-% Isopar G mit Hilfe eines Schnellrührers dispergiert. Die Dispersion wurde mit3 g of a dispersion consisting of 33% by weight of the microencapsulated diuron in Example 2 and 77% by weight of Isopar G were dissolved in 11.67 g of a silicone resin solution with a viscosity of 3,000 mPas, consisting of 77.1% by weight. % of a high molecular weight, physically drying organopolysiloxane and 22.9% by weight of Isopar G using a high-speed stirrer. The dispersion was with
Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde 10 h bei 60°C getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 150 μm. Beispiel 7Using a doctor blade with a wet film thickness of 250 μm applied to an epoxy coated metal plate. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 μm was obtained. Example 7
Erfindungsgemäße BeschichtungCoating according to the invention
11,67 g einer Siliconharzlösung mit einer Viskosität von 3 000 mPas, bestehend aus 77,1 Gew.-% eines hochmolekularen, physikalisch trocknenden Organopoly- siloxans und 22,9 Gew.-% Isopar G wurde mit 4 g Isopar G verdünnt. In dieser11.67 g of a silicone resin solution with a viscosity of 3,000 mPas, consisting of 77.1% by weight of a high molecular weight, physically drying organopolysiloxane and 22.9% by weight of Isopar G, was diluted with 4 g of Isopar G. In this
Lösung wurden 1 g des in Beispiel 1 mikroverkapselten Diurons mit Hilfe eines Schnellrührers dispergiert. Die Dispersion wurde mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde 10 h bei 60°C getrocknet. Man erhielt eine homo- gene Beschichtung mit einer Schichtdicke von ca. 150 μm.Solution 1 g of the microencapsulated diuron in Example 1 was dispersed using a high-speed stirrer. The dispersion was applied with the aid of a doctor blade with a wet film thickness of 250 μm to a metal plate coated with epoxy paint. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 μm was obtained.
Beispiel 8Example 8
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie Beispiel 7. Es wurde jedoch 1 g des in Beispiel 3 mikroverkapselten Alsystins in der verdünnten Siliconharzlösung dispergiert.The same procedure as in Example 7. However, 1 g of the Alsystin microencapsulated in Example 3 was dispersed in the dilute silicone resin solution.
Beispiel 9Example 9
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie Beispiel 7. Es wurde jedoch eine Mischung, bestehend aus 0,5 g des in Beispiel 1 mikroverkapseltem Diurons und 0,5 g des in Beispiel 3 mikroverkapselten Alsystin in der verdünnten Siliconharzllösung dispergiert.The same procedure as Example 7. However, a mixture consisting of 0.5 g of the microencapsulated diuron in Example 1 and 0.5 g of the microencapsulated Alsystin in Example 3 was dispersed in the dilute silicone resin solution.
Beispiel 10Example 10
VergleichsbeispielComparative example
1 1,67 g Siliconharzlösung mit einer Viskosität von 3 000 mPas, bestehend aus 77,1 Gew.-% eines hochmolekularen, physikalisch trocknenden Organopolysiloxans und 22,9 Gew.-% Isopar G wurde mit 4 g Isopar G verdünnt. Die Harz- lösung wurde mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine1 1.67 g of silicone resin solution with a viscosity of 3,000 mPas, consisting of 77.1% by weight of a high molecular weight, physically drying organopolysiloxane and 22.9% by weight of Isopar G, was diluted with 4 g of Isopar G. The resin solution was applied using a doctor blade with a wet film thickness of 250 μm
Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde 10 h bei 60°C getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 150 μm. Beispiel 11Epoxy paint coated metal plate applied. The coating was dried at 60 ° C for 10 h. A homogeneous coating with a layer thickness of approximately 150 μm was obtained. Example 11
Erfindungsgemäße BeschichtungCoating according to the invention
In 26,7 g eines OH-funktionellen Polyoxyalkylen-Polynethylsiloxan-Copolymeren wurden mit Hilfe eines Schnellrührers 6 g Diuron, 1,8 g Baysilone®-Lack- additiv PL (erhältlich bei der Bayer AG) und 0,12 g Baysilone®-Lackadditiv Versuchsprodukt AI 3465 (erhältlich bei der Bayer AG) dispergiert. Die Dispersion wurde mit 27,3 g Polyisocyanat-Prepolymer (Desmodur E 21, erhältlich bei der Bayer AG) versetzt und mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde bei Raumtemperatur getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 250 μm.6 g of diuron, 1.8 g of Baysilone ® lacquer additive PL (available from Bayer AG) and 0.12 g of Baysilone ® lacquer additive were added to 26.7 g of an OH-functional polyoxyalkylene-polyethylsiloxane copolymer using a high-speed stirrer Experimental product AI 3465 (available from Bayer AG) dispersed. The dispersion was mixed with 27.3 g of polyisocyanate prepolymer (Desmodur E 21, available from Bayer AG) and applied to an epoxy-coated metal plate using a doctor blade with a wet film thickness of 250 μm. The coating was dried at room temperature. A homogeneous coating with a layer thickness of approximately 250 μm was obtained.
Beispiel 12Example 12
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 11. Als Biozid wurden jedoch 6,0 g Alsystin eingesetzt.The same procedure as in Example 11. However, 6.0 g of Alsystin were used as the biocide.
Beispiel 13Example 13
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 11. Als Biozid wurden jedoch 6,0 g des in Beispiel 2 mikroverkapselten Diurons eingesetzt.The same procedure as in Example 11. However, 6.0 g of the microencapsulated diuron in Example 2 were used as the biocide.
Beispiel 14Example 14
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 11. Als Biozid wurden jedoch 6,0 g des in Beispiel 3 mikroverkapselten Alsystin eingesetzt.The same procedure as in Example 11. However, 6.0 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
Beispiel 15 VergleichsbeispielExample 15 Comparative Example
Gleiches Vorgehen wie in Beispiel 11. Es wurde jedoch kein Biozid eingesetzt. Beispiel 16The same procedure as in Example 11. However, no biocide was used. Example 16
Erfindungsgemäße BeschichtungCoating according to the invention
In 27 g eines linearen ,ω-Dihydroxypolydimethylsiloxans mit einer Viskosität von ca. 500 mPas wurden mit Hilfe eines Schnellrührers 3 g Diuron dispergiert. Die Dispersion wurde mit 0,81 Vernetzer C5 (erhältlich bei der Bayer AG) versetzt und mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde bei Raumtemperatur getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 250 μm.3 g of diuron were dispersed in 27 g of a linear, ω-dihydroxypolydimethylsiloxane with a viscosity of approx. 500 mPas using a high-speed stirrer. The dispersion was mixed with 0.81 crosslinker C5 (available from Bayer AG) and applied with the aid of a doctor blade with a wet film thickness of 250 μm to an epoxy lacquered metal plate. The coating was dried at room temperature. A homogeneous coating with a layer thickness of approximately 250 μm was obtained.
Beispiel 17Example 17
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 16. Als Biozid wurden jedoch 6,0 g Alsystin eingesetzt.The same procedure as in Example 16. However, 6.0 g of Alsystin were used as the biocide.
Beispiel 18 Erfindungsgemäße BeschichtungExample 18 Coating According to the Invention
Gleiches Vorgehen wie in Beispiel 16. Als Biozid wurden jedoch 3 g des in Beispiel 2 mikroverkapselten Diurons eingesetzt.The same procedure as in Example 16. However, 3 g of the microencapsulated diuron in Example 2 were used as the biocide.
Beispiel 19Example 19
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 16. Als Biozid wurden jedoch 3 g des inThe same procedure as in Example 16. However, 3 g of the in
Beispiel 3 mikroverkapselten Alsystins eingesetzt.Example 3 microencapsulated Alsystins used.
Beispiel 20 VergleichsbeispielExample 20 Comparative Example
Gleiches Vorgehen wie in Beispiel 16. Es wurde jedoch kein Biozid eingesetzt. Beispiel 21The same procedure as in Example 16. However, no biocide was used. Example 21
Erfindungsgemäße BeschichtungCoating according to the invention
In 27 g einer vinylgruppenhalügen Polymethylsiloxanmischung (Silopren® U Grundmischung H6, erhältlich bei der Bayer AG) werden mit Hilfe eines Schnellrührers 3 g Diuron dispergiert. Die Dispersion wurde mit 1,81 g eines SiH- haltigen Vernetzers (Silopren® U Vernetzer 830, erhältlich bei der Bayer AG) und 0,027 g eines Pt-Katalysators (Silopren® U Katalysator Pt/S. erhältlich bei der Bayer AG) versetzt und mit Hilfe einer Rakel mit einer Naßfilmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde bei Raumtemperatur getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 250 μm.In 27 g of a vinylgruppenhalügen Polymethylsiloxanmischung (Silopren U ® basic mixture H6, available from Bayer AG) are dispersed using a high-speed 3 g diuron. The dispersion was mixed with 1.81 g of a SiH-containing crosslinking agent (Silopren U crosslinker ® 830, available from Bayer AG) and 0.027 g of a Pt catalyst (Pt catalyst Silopren ® U / S. Available from Bayer AG) was added and applied with the aid of a doctor blade with a wet film thickness of 250 μm on an epoxy lacquered metal plate. The coating was dried at room temperature. A homogeneous coating with a layer thickness of approximately 250 μm was obtained.
Beispiel 22Example 22
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 21. Als Biozid wurden jedoch 3 g Alsystin ein- gesetzt.The same procedure as in Example 21. However, 3 g of Alsystin were used as the biocide.
Beispiel 23Example 23
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 21. Als Biozid wurden jedoch 3 g des in Beispiel 2 mikroverkapselten Diurons eingesetzt.The same procedure as in Example 21. However, 3 g of the microencapsulated diuron in Example 2 were used as the biocide.
Beispiel 24Example 24
Erfindungsgemäße BeschichtungCoating according to the invention
Gleiches Vorgehen wie in Beispiel 21. Als Biozid wurden jedoch 3 g des in Beispiel 3 mikroverkapselten Alsystins eingesetzt.The same procedure as in Example 21. However, 3 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
Beispiel 25 VergleichsbeispielExample 25 Comparative Example
Gleiches Vorgehen wie in Beispiel 21. Es wurde jedoch kein Biozid eingesetzt. Beispiel 26The same procedure as in Example 21. However, no biocide was used. Example 26
Erfindungsgemäße BeschichtungCoating according to the invention
In 30,2 g einer Lösung eines Siliconacrylat-Copolymeren (Baysilone® Imprägniermittel LF, erhältlich bei der Bayer AG) wurden mit Hilfe eines Schnellrührers 2 g Alsystin dispergiert. Mit Hilfe einer Rakel wurde die Dispersion mit einer Naß- filmdicke von 250 μm auf eine Epoxidlack beschichtete Metallplatte aufgetragen. Die Beschichtung wurde bei Raumtemperatur getrocknet. Man erhielt eine homogene Beschichtung mit einer Schichtdicke von ca. 155 μm.In 30.2 g of a solution of a silicone acrylate copolymer (Baysilone ® impregnating LF, available from Bayer AG) were dispersed a high-speed 2 g Alsystin using. With the help of a doctor blade, the dispersion was applied with a wet film thickness of 250 μm to an epoxy coated metal plate. The coating was dried at room temperature. A homogeneous coating with a layer thickness of approximately 155 μm was obtained.
Beispiel 27 Erfindungsgemäße BeschichtungExample 27 Coating According to the Invention
Gleiches Vorgehen wie in Beispiel 26. Als Biozid wurden jedoch 2 g des in Beispiel 3 mikroverkapselten Alsystins eingesetzt.The same procedure as in Example 26. However, 2 g of the microencapsulated Alsystin in Example 3 were used as the biocide.
Beispiel 28 VergleichsbeispielExample 28 Comparative Example
Gleiches Vorgehen wie in Beispiel 21. Es wurde jedoch kein Biozid eingesetzt. The same procedure as in Example 21. However, no biocide was used.
Anwendungsbeispiele 29-33 zur Prüfung der Anheftung von benthischen Kieselalgen (Nitzschia pusilla) an erfindungsgemäße BeschichtungenApplication examples 29-33 for testing the attachment of benthic diatoms (Nitzschia pusilla) to coatings according to the invention
Testorganismus: Kieselalge Nitzschia (benthischen Kieselalge) Medium: ASW-Medium Kulturgefäße: Erlenmeyer-Kulturkolben Testbedingungen: Temperatur: 18°C, künstliches Dauerlicht, permanente Bewegung auf einem Taumelschüttler, ohne Zusatzbelüftung.Test organism: Diatom Nitzschia (benthic diatom) Medium: ASW medium Culture vessels: Erlenmeyer culture flasks Test conditions: Temperature: 18 ° C, artificial continuous light, permanent movement on a tumbler, without additional ventilation.
Auswertung: Vergleich der erfindungsgemäßen Beschichtungen bezüglich Bewuchs mit Vergleichsbeispiel 10 und einer mit Epoxidlack beschichteten Metallplatte. Der Grad des Bewuchses wird folgendermaßen gekennzeichnet:Evaluation: Comparison of the coatings according to the invention with respect to fouling with comparative example 10 and a metal plate coated with epoxy paint. The degree of growth is identified as follows:
gleichmäßig guter Bewuchs geringer Bewuchsuniformly good growth low growth
+ ganz geringer Bewuchs kein Bewuchs+ very little growth no growth
Ergebnis der Anwendungsbeispiele: Result of the application examples:
Die erfindungsgemäße Beschichtung aus Beispiel 4 enthielt ein Organopolysiloxan als Bindemittel und Diuron als abbaubares Biozid. Nach 14 Tagen Exposition dieser Beschichtung mit benthischen Kieselalgen bei 18°C, künstlichem Dauerlicht permanenter Bewegung und ohne Zusatzbelüftung war nur ein ganz geringerThe coating according to the invention from Example 4 contained an organopolysiloxane as a binder and diuron as a degradable biocide. After 14 days of exposure of this coating to benthic diatoms at 18 ° C, artificial continuous light, permanent movement and without additional ventilation, there was only a very small one
Bewuchs (+) vorhanden.There is vegetation (+).
Ebenfalls nur ganz geringen Bewuchs (+) zeigte in Beispiel 30 die erfindungsgemäße Beschichtung aus Beispiel 5. Sie enthielt ein Organopolysiloxan als Bindemittel und Alystin als abbaubares Biozid.The coating according to the invention from example 5 likewise showed only very slight fouling (+) in example 30. It contained an organopolysiloxane as binder and alystin as degradable biocide.
Kein Bewuchs (-) unter den angegebenen Testbedingungen zeigte die erfindungsgemäße Beschichtung aus Beispiel 9. Sie enthielt als Bindemittel ebenfalls ein Organopolysiloxan und als abbaubare Biozide eine Mischung aus mikrover- kapseltem Diuron und mikroverkapseltem Alystin. Dies ist insofern überraschend, da die Biozide zur Erzielung einer guten Langzeitwirkung mikroverkapselt waren.The coating according to the invention from Example 9 showed no fouling (-) under the test conditions indicated. It also contained an organopolysiloxane as a binder and a mixture of microencapsulated diuron and microencapsulated alystin as degradable biocides. This is surprising in that the biocides were microencapsulated for good long-term effects.
Die Beschichtung aus Vergleichsbeispiel 10 war biozidfrei. Das Bindemittel war ein Organopolysiloxan. Diese Beschichtung zeigte in Beispiel 32 geringen Bewuchs (++). Eine mit einem Epoxidlack beschichtete Metallplatte zeige dagegen in Beispiel 33 einen gleichmäßig guten Bewuchs (+++). The coating from comparative example 10 was biocide-free. The binder was an organopolysiloxane. In Example 32, this coating showed low growth (++). In contrast, a metal plate coated with an epoxy varnish shows in Example 33 a uniformly good growth (+++).

Claims

Patentansprüche claims
1. Mittel enthaltend a) mindestens ein Organopolysiloxan und b) mindestens ein schwermetallfreies Biozid.1. Agent containing a) at least one organopolysiloxane and b) at least one heavy metal-free biocide.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die Biozide in Seewasser abbaubar sind.2. Composition according to claim 1, characterized in that the biocides are degradable in sea water.
3. Mittel nach Anspruch 2, dadurch gekennzeichnet, daß die Biozide im Meerwasser bei 25°C eine Halbwertszeit von weniger als 180 Tagen aufweisen.3. Composition according to claim 2, characterized in that the biocides in sea water at 25 ° C have a half-life of less than 180 days.
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekenn- zeichnet, daß die Biozide mikroverkapselt sind.4. Composition according to one or more of claims 1 to 3, characterized in that the biocides are microencapsulated.
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Organopolysiloxan ein hochmolekulares Siliconharz der Formel5. 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 formula
R (R *Q) b Si(0) (4,(,+b)) _R (R * Q) b Si (0) (4 , ( , + b)) _
2 wobei2 where
R1 für einen einwertigen Kohlenwasserstoffrest mit 1 - 14 C- Atomen der gegen Wasser inerte Substituenten aufweisen kann,R 1 is a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may have substituents which are inert to water,
R2 für einen einwertigen Kohlenwasserstoffrest mit 1 - 5 C-Atomen steht,R 2 stands for a monovalent hydrocarbon radical with 1-5 C atoms,
a = 0, 1, 2 oder 3, durchschnittlich 0,75 - 1,5 und b = 0, 1, 2, 3, durchschnittlich 0,01 - 0,1 bedeutet,a = 0, 1, 2 or 3, mean 0.75 - 1.5 and b = 0, 1, 2, 3, mean 0.01 - 0.1,
6. Mittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Organopolysiloxan ein niedermolekulares alkoxyfunk- tionelles Siliconharz der Formel R x (R40)v Si(0) (4-(x+ y»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 formula R x (R 4 0) v Si (0) (4- (x + y »
wobeiin which
R3 für einen einwertigen Kohlenwasserstoffrest mit 1 - 14 C-Atomen der gegen Wasser inerte Substituenten aufweisen kann,R 3 is a monovalent hydrocarbon radical having 1 to 14 carbon atoms which may have substituents which are inert to water,
R4 für einen einwertigen Kohlenwasserstoffrest mit 1 - 5 C-Atomen steht,R 4 represents a monovalent hydrocarbon radical with 1 to 5 carbon atoms,
x = 0, 1, 2 oder 3, durchschnittlich 0,75 - 1,5 undx = 0, 1, 2 or 3, average 0.75 - 1.5 and
y = 0, 1, 2, 3, durchschnittlich 0,2 - 2,0 bedeutet,y = 0, 1, 2, 3, means 0.2 - 2.0 on average,
ist.is.
7. Mittel nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Organopolysiloxan ein Silicon-Kautschuk ist.7. Composition according to one or more of claims 1 to 6, characterized in that the organopolysiloxane is a silicone rubber.
8. Mittel nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Organopolysiloxan endständige und/oder seitenständige organofunktionelle Reste enthält.8. Composition according to one or more of claims 1 to 7, characterized in that the organopolysiloxane contains terminal and / or lateral organofunctional radicals.
9. Mittel nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Organopolysiloxan ein Organosilicon Copolymersystem ist.9. Composition according to one or more of claims 1 to 8, characterized in that the organopolysiloxane is an organosilicone copolymer system.
10. Mittel nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Mittel zusätzlich anorganische Pigmente, organische Pigmente, Farbstoffe, welche vorzugsweise in Seewasser unlöslich sind, und/oder übliche Hilfsmittel wie Füllstoffe, Lösungsmittel, Weichmacher, Katalysatoren, Inhibitoren, Haftmittel, Lackadditive und/oder gängige Dis- pergierhilfsmittel enthält.10. Agent according to one or more of claims 1 to 9, characterized in that the agents additionally inorganic pigments, organic pigments, dyes, which are preferably insoluble in sea water, and / or conventional auxiliaries such as fillers, solvents, plasticizers, catalysts, inhibitors , Contains adhesives, paint additives and / or common dispersing agents.
11. Verwendung von a) mindestens einem Organopolysiloxan und b) minde- stens einem schwermetallfreien Biozid zur Herstellung von Antifouling- mitteln und Antifoulingbeschichtungen. 11. Use of a) at least one organopolysiloxane and b) at least one heavy metal-free biocide for the production of antifouling agents and antifouling coatings.
12. Verfahren zur Herstellung von Antifoulingmitteln, dadurch gekennzeichnet, daß man die für Antifoulingmittel verwendbaren Bestandteile mit a) mindestens einem Organopolysiloxan und b) mindestens einem schwermetallfreien Biozid versetzt.12. A process for the preparation of antifouling agents, characterized in that a) at least one organopolysiloxane and b) at least one heavy metal-free biocide are added to the constituents which can be used for antifouling agents.
13. Die nach dem Verfahren gemäß Anspruch 11 erhältlichen Antifoulingmittel.13. The antifouling agents obtainable by the process according to claim 11.
14. Verfahren zur Herstellung von Antifoulingbeschichtungen, dadurch gekennzeichnet, daß man ein Mittel enthaltend mindestens ein Organopolysiloxan und mindestens ein schwermetallfreies Biozid auf die zu schützenden Gegenstände aufträgt. 14. A method for producing antifouling coatings, characterized in that an agent containing at least one organopolysiloxane and at least one heavy metal-free biocide is applied to the objects to be protected.
EP97912174A 1996-10-24 1997-10-13 Antifouling paints Withdrawn EP0934367A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19644225A DE19644225A1 (en) 1996-10-24 1996-10-24 Antifouling coating
DE19644225 1996-10-24
PCT/EP1997/005626 WO1998017732A1 (en) 1996-10-24 1997-10-13 Antifouling paints

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KR (1) KR20000049020A (en)
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AU (1) AU729165B2 (en)
BR (1) BR9712996A (en)
CA (1) CA2269528A1 (en)
DE (1) DE19644225A1 (en)
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WO (1) WO1998017732A1 (en)

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NO991877D0 (en) 1999-04-20
JP2001502732A (en) 2001-02-27
AU4947097A (en) 1998-05-15
US6291549B1 (en) 2001-09-18
WO1998017732A1 (en) 1998-04-30
NO991877L (en) 1999-04-20
KR20000049020A (en) 2000-07-25
DE19644225A1 (en) 1998-04-30
CN1234059A (en) 1999-11-03
BR9712996A (en) 2000-04-18
CA2269528A1 (en) 1998-04-30
AU729165B2 (en) 2001-01-25

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