AU736095B2 - Algicides - Google Patents

Description

WO 98/51154 PCT/EP98/0261.7 -1I- AIR cides The present invention relates to the novel use of a mixture of at least two of the known active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin, and mixtures of these active substances optionally with other known active substances that provide a synergistic complement for the control of algal infestation of architectural plants, antifouling paints and other industrial materials.

N J]-NHCH 3

H

0 Benzthiazuron 0 N

JY-NHCH

3 S

CH

3 Methabenzthiazuron Tebuthiuron -2-

CH

CH

3 Isoproturon

NH

2 Ethiozin

S

S

*5e5

S*

C

It has already been disclosed that broad-leaved weeds can be controlled selectively with benzthiazuron and methabenzthiazuron (cf. e.g. BE Patent 687019; US 2 756 135; GB 1 085 430).

It is also known that broad-leaved weeds can be controlled with tebuthiuron (cf.

DE 1 816 568) and ethiozin (cf. US 3 671 523).

Isoproturon is likewise employed to control unwanted broad-leaved weed growth 15 (see e.g. DE 2 039 041).

Furthermore, in the course of studies of the environmental behaviour of isoproturon, the activity with respect to some freshwater algae has been disclosed (see M. Manthey et al., Sci. Total Environ. 1993, pp. 453-459; F.A. Anton et al., Sci.

Total Environ. 1993, pp. 845-851; J.I.N. Kumar, J. Indian Bot. Soc. 70, 277 (1991)).

It has now unexpectedly been found that a mixture of at least two of the active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are also suitable for the control of algal infestation of architectural paints, antifouling paints and other industrial materials. This is particularly unexpected because the said active substances can also be used to control the blue algae that are relevant in coating systems.

It has additionally been found that the said active substances are not leached from the media to be protected (marine paints, emulsion paints, etc.) and hence lead to an outstanding long-term effect. The active substances possess long-term stability in both the commercially customary paint and the paint which has been applied and dried.

Owing to the good algicidal activity, the compounds of the invention are also active against lichens. In combination with fungicides, there is a synergistic increase in the level of action in this case.

It has additionally been found that the action of a mixture of at least two of the known active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin can also be improved considerably, in some cases even synergistically, by mixing in further herbicides, algicides and/or material-protectants as co-components.

Thus, in accordance with the present invention there is provided a method for i controlling algal growth on industrial materials comprising admixing or treating said industrial materials with a mixture of at least two compounds selected from the group consisting of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon, and S 25 ethiozin, wherein the industrial materials are selected from the group consisting of interior emulsion paints, exterior emulsion paints, antifouling paints, wood preservative paints, stains, varnishes, polymer coatings, latices, adhesives, glues and textiles.

In accordance with another aspect of the present invention there is provided a composition comprising an industrial material containing a mixture of at least two components selected from the group consisting of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon, and P:\WPDOCS\CRN\SPECI\749588.spe.doc-2A/01 -3aethiozin in an admixture with at least one active substance that provides a synergistic complement for the control of algae, wherein the industrial material is selected from the group consisting of interior emulsion paints, exterior emulsion paints, antifouling paints, wood preservative paints, stains, varnishes, polymer coatings, latices, adhesives, glues and textiles.

The algae to be controlled preferably comprise prokaryotic algae (Cyanophyta/blue algae) such as, for example, representatives of the subclass Coccogoneae and of the subclass Hormogoneae.

By way of example but not limitation mention may be made, from the order of the Chroococcales, of species of the genera Synechococcus, Chroococcus, Gloeocapsa, Aphanocapsa, Aphanothece, Microcystis and Merismopedia; from the orders of the Chamaesiphonales and Pleurocapsales, of species of the genera Chamaesiphon and Dermatocarpa; from the order of the Oscillatoriales, of species of the genera Phormidium, Schizothrix, Spirulina, Plectonema and Lyngbya; from the order of the Nostocares, of species of the genera Nostoc, Rivularia, Tolypothrix, Scytonema, S* o**oe -4- Anabaenopsis, Calothrix and Aulosira; and, from the order of the Stigonematatles, of species of the genera Stigonema, Fischerella, Hapalosiphon and Mastigocladus.

Furthermore, the compounds also exhibit a good activity against eukaryotic representatives from the divisions Heterokontophyta, Rhodophyta, Chlorophyta, Euglenophyta, Cryptophyta, Dinophyta and Haptophyta. By way of example bdt without being restrictive mention may be made, from the class of the Xanthophyceae, of species of the genera Tribonema and Vaucheria; from the class of the Chrysophyceae, of species of the genera Chrysocapsa, Rhizochrysis, Cfhrysosphaera, Phaeothamnion and Thallochrysis; from the class of the Phaeophyceae (brown algae), of species of the genera Ectocarpus, Pylaiella, Cutleria, Zanardinia, Dictyota, Padina, Dictyopteris, Laminaria, Macrocystis, Lessonia, Nerocystis, Chorda, Alaria, Fucus, Ascophyllum, Himanthalia, Sargassum, Cystoseira, Halidrys, Pelvetia, Coccophora and Durvilla; from the class of the Rhodophyceae (red algae), of species of the genera Porphyridum, Bangia, Porphyra, "Corallina, Lithothamnia, Lithophyllum, Rhodymania, Delesseria, Grinnellia, Platysiphonia, Polysiphonia, Ceramium and Plumaria; and, from the class of the Chlorophyceae (green algae), of species of the genera Chlorococcum, Chlorella, Spongiochloris, Monostroma, Ulva, Enteromorpha, Ulothrix, Trentepohlia, 20 Apatococcus, Desmococcus, Cladophora, Siphonocladus, Valonia, Caulerpa, Bryopsis, Acetabularia, Halimeda and Tuna.

The industrial materials or media to be given an algicidal treatment .0 comprise wood preservative paints, stains and varnishes, polymer coatings, latices, 25 adhesives, glue and textiles, and especially interior and exterior emulsion paints and antifouling paints.

By emulsion paints are meant aqueous, alkaline formulations of coating materials based on polymer dispersions, which act as binders. The polymer dispersions used to prepare emulsion paints comprise by way of example and preferably polyacrylates, styrene acrylates, polyvinyl acetate, polyvinyl propionate, and other polymers.

Benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin are incorporated either directly or in the form of formulations or mixtures into the abovementioned emulsion paints or into the starting materials for them.

Antifouling paints consist in general of the constituents described in Ungerer, Chem.

Ind. 37 (1985), 730-732 and Williams, Antifouling Marin Coatings 1973, Park Ridge: Noyes 1973.

Examples of acknowledged binders in antifouling paints are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system especially in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/styrene rubbers, butadiene/acrylonitrile rubbers, butadiene/styrene/acrylonitrile rubbers, drying oils, such as linseed oil, asphalt, and also epoxy compounds, resin esters or modified hard resins in combination with tar or bitumens, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

The antifouling compositions also optionally include inorganic pigments, organic pigments or dyes, which are preferably insoluble in salt water. The antifouling compositions may also comprise materials such as rosin. These materials, in the case of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin, bring about controlled release of the active substances. The antifouling compositions may also include plasticizers, modifying agents which influence the rheological properties, and other conventional constituents. Benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin are incorporated either directly or as a formulation/mixture into the abovementioned antifouling paints or into the starting materials for them. Benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin can also be incorporated into self-polishing antifouling systems, as, for example, into the combinations mentioned below.

For their incorporation into the industrial materials, benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are preferably in the form -6of customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, and forms in which they are encapsulated very finely in polymeric substances.

These formulations and compositions are prepared in a known manner, for example by mixing the active substances with extenders: that is, liquid solvents, pressurized liquefied gases and/or solid carriers, with or without the use of surface-active agents: that is, emulsifiers and/or dispersants and/or foam-forming agents. In the case of the use of water as an extender it is also possible, for example, to use organic solvents as auxiliary solvents. Suitable liquid solvents are essentially aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. mineral oil fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulphoxide, and also water; by liquefied gaseous extenders or carriers are meant those liquids which are gaseous at standard temperature and under standard pressure, examples being aerosol propellants, such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide; suitable solid carriers are, for example, natural ground minerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic ground minerals, such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and also synthetic granules made from organic and inorganic flours and also granules of organic materials such as sawdust, coconut husks, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, and also protein hydrolysates; suitable dispersants are, for example, lignin-sulphite waste liquors and methylcellulose.

In the formulations it is possible to use tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The present invention additionally provides synergistically acting mixtures of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin with at least one fungicide and optionally further active substances.

The activity against algae and the spectrum of action of the active substances of the invention and/or of formulations prepared from them is also increased if further algicidal compounds, bactericides, molluscicides, insecticides and/or antifouling agents are added. The mixtures possess a broader spectrum of action than the individual active substances alone.

In many cases, the effects obtained with the use of these mixtures are also synergistic; in other words, the activity of the mixture is greater than the activity of the individual components. Particularly suitable co-components are, for example, the following compounds: Triazoles such as: azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole,, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fenchiorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazol, penconazole, propioconazole, (±)-cis-l1-(4-chlorophenyl)-2-( 1H- 1,2,4triazol- 1-yl)-cycloheptanol, 2-(l1-tert-butyl)- 1-(2-chlorophenyl)-3-( 1,2,4-triazol- 1-yl)propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts; Imidazoles such as: clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lomnbazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar, 1 -imidazolyl-l1-(4'-chlorophenoxy)-3 ,3-dimethylbutan-2-one and their metal salts and acid adducts; Pyridines and pyrimidines such as: ancymidol, buthiobate, fenarimol, nuarimol, triamirol; Succinate dehydrogenase inhibitors such as: benodanil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, furcarbanil, furmecyclox, mebenil, mepronil, methfuroxam, metsulfovax, pyrocarbolid, oxycarboxin, Shirlan, Seedvax; Naphthalene derivatives such as: terbinafine, naftifine, butenafine, 3 -chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine); Suiphenamides such as: dichlorfluanid, tolylfluanid, folpet, fluorfolpet; captan, captofol; Benzimidazoles such as: carbendazim, benomyl, fuiberidazole, thiabendazole or salts thereof; Morpholine derivates such as: aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin fenpropimorph, tridemorph, trimorphamide and their salts with arylsuiphonic acids, such as e.g.

p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid; Beozothiazoles such as: 2-mercaptobenzothiazole; Benzothiophene dioxides such as: benzo[b]thiophene S,S-dioxide carboxylic acid cyclohexyl amide; Benzamides such as: 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, tecloftalam; Boron compounds such as: boric acid, borates, borax; Formaldehyde and formaldehyde donor compounds such as: benzyl alcohol mono-(poly)-hemiformnal, n-butanol hemniformal, dazomet, ethylene glycol hemniformal, hexa-hydro-S-triazines, hexamethylenetetramine, N-hydroxymethyl-N '-methylthiourea, N-methylolchloroacetamide, oxazolidines, paraformaldehyde, tauroline, tetrahydro- 1 ,3-oxazine, N-(2-hydroxypropyl)-aminemethanol; Isothiazolinones such as: N-methylisothiazolin-3 -one, 5-chloro-N-methylisothiazolin-3 -one, octyli sothiazolin-3 -one, 5-chloro-N-octylisothiazolinone, N-octyl-isothiazolin-3-one, Aldehydes such as: cinnamaldehyde, formaldehyde, glutardialdehyde, f0-bromocinnamaldehyde; Thiocyanates such as: thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate; Quaternary ammonium compounds such as: benzalkoniumn chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyl-dimethyl-alkyl-amnioniumchloride, didecyldimethylanimonium chloride, dioctyl-dimethyl-amnmonium chloride, N-hex adecyl-trimethyl-ammonium chloride, 1 -hexadecyl-pyridinium chloride; Iodine derivates such as: diiodomethyl-p-tolyl sulphone, 3-iodo-2-propinyl-alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyl n-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbaniate; Phenols such as: tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3 ,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, 2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol, hexachlorophen, p-hydroxybenzoic esters, o-phenylphenol, m-phenylphenol, p-phenylphenol and their alkali metal salts and alkaline earth metal salts; Microbicides having an activated halogen group such as: bronopol, bronidox, 2-bromo-2-nitro- 1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 1 -bromo-3-chloro-4,4,5 ,5-tetramethyl-2-imidazoldinones, 0 -bromo- P -nitrostyrene, chioroacetamide, chloramine T, 1 ,3-dibromo-4,4,5,5-tetrametyl-2-imidazoldinones, dichloramine T, 3 ,4-dichloro-(3H)- 1 ,2-dithiol-3 -one, 2,2-dibromo-3-nitrilpropionan-ide, 1 ,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid,

-II-

phenyl 2-chiorocyanovinyl suiphone, phenyl 1 ,2-dichloro-2-cyanovinyl suiphone, trichioroisocyanuric acid; Pyridines such as: 1 -hydroxy-2-pyridinethione (and the Na, Fe, Mn, Zn salts thereof), tetrachloro-4methyl sulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, I -hydroxy-4methyl-6-(2,4,4-trimethylpentyl)-2( 1H)-pyridine; Methoxyacrylates or the like such as: methyl (E)-methoximino [alpha-(o-tolyloxy)-o-tolyl] acetate, 2 -methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide, {2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy~phenyl }-3-methoxyacrylate, O-methyl-2-[([3 -methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximinoacetimi.

date, 2 ,5 -dimethylphenyl)ethylidene] amino] oxy]methyl] alpha.-(methoximino)- N\-metyl-benzeneacetamnide, alpha-(methoxyimino)-N-methyl-2-[[[[l1-[3-(trifluoromethyl)phenyl]ethylidene]amnino]oxy]methyl]-benzeneacetamide, alpha-(methoxyimino)-2-[ -[3-(trifluoromethyl)phenyl]ethylidene] amino] oxy]methyl]..benzeneacetic acid methyl ester, alpha-(methoxymethylene)-2-[ -[3-(trifluoromethyl)phenyl]ethylidene] amino] oxy]methyl] -benzeneacetic acid methyl ester, [-chloro-3-(trifluormnethyl)-2-pyridinyl]oxy]methyl] alpha.-(methoxyimino)-Nmethyl-benzeneacetamide, [cyclopropyl [(4-ethoxyphenyl)imino] methyl]thio]methyl] alpha. (methoxyimino)-benzeneacetic acid methyl ester, alpha-(methoxyimino)-N-methyl2(4methylsphenyl.2,7-dioxa-3,6-diazaocta-3 dien- 1 -yl)-benzeneacetamide, alpha-(methoxymethylene)-2-(4-methyl-5-phenyl.2,7..dioxa-3,6-diazaocta-3,5-dien- 1-yl)-benzeneacetic acid methyl ester, alpha-(methoxyimino)-N-methyl-2-[[[ 1-13-(trifluoromethyl)phenyl] ethoxy] imino]methyl]-benzeneacetamide, 12 2- -dichloro-2-pyridinyl)oxy]methyl] alpha. -(methoxyimino)-N-methyl.

benzeneacetamide, 2-[4,5-dimethyl-9-(4-morpholinyl)-2,7-dioxa-3 ,6-diazanona-3,5-dien- Il-yl] alpha.- (methoxymethylene)-benzeneacetic acid methyl ester; Metal soaps such as: the naphthenates, octoates, 2-ethyihexanoates, oleates, phosphates and benzoates of tin, copper and zinc; Metal salts such as: copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate; Oxides such as: tributyltin oxide, Cu 2 O, CuO, ZnO; Dithiocarbamates such as: cufraneb, ferban, potassium N-hydroxymethyl-N '-methyl-dithiobarbamate, Na or K dimethyldithiocarbamate, macozeb, maneb, metam, metiram, thiram, zineb, ziram; Nitriles such as: 2,4,5 ,6-tetrachloroisophthalodinitrile, disodiumn cyano-dithioimidocarbamate; Quinolines such as: 8-hydroxyquinoline and its Cu salts; 13 Other fungicides and bactericides such as: 5-hydroxy-2(5H)-fuiranone; 4,5-benzodithiazolinone, 4

N-(

2 -p-chlorobenzoylethyl)-hexaminium chloride, 2 -oxo- 2 4 -hydroxy-phenyl)acethydroximic chloride, tris-N-(cyclohexyldiazeniumdioxy)yaluminium, N-(cyclo-hexyldiazeniumdioxy)-tributyltin and K salts, bis-N-(cyclohexyldiazeniumdioxy).copper; Ag, Zn or Cu-containing zeolites alone or enclosed in polymeric materials.

Insecticides acaricides nemnaticides such as: abamnectin, acephat, acetamniprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, alpha-cypermethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, barthrin, 4 -bromo-2(4-chlorophenyl)- fluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, bioresmethrin, bioallethrin, bromophos A, bromophos M, bufencarb, buprofezin, butathiophos, butocarboxin, butoxycarboxim, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chinomethionat, cloethocarb, chlordane, chiorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, 6 -chloro- 3 -pyridinyl)-methylpN'-cyano-N..methyl-ethanimidamide, chiorpicrin, chlorpyrifos A, chiorpyrifos M, cis-resmethrin, clocythrin, cypophenothrin clofentezin, coumaphos, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin, decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, dialiphos, diazinon, 1 ,2-dibenzoyl- 1(1,1 -dimethyl)-hydrazine,

DNOC,

dichlofenthion, dichlorvos, dicliphos, dicrotophos, diflubenzuron, dimethoate, dimethyl-(phenyl)-silyl-methyl 3-phenoxybenzyl ether, dimethyl-(4-ethoxyphenyl)silylmethyl. 3-phenoxybenzyl ether, dimethylvinphos, dioxathion, disulfoton, -14eflusilanate, emamectin, empenthrin, endosulfan, EPN, esfenvalerat, ethiofencarb, ethion, ethofenprox, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximat, fensulfothion, fenthion, fenvalerate, fipronil, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flumethrin flufenprox, fluvalinate, fonophos, formethanate, formothion, fosmethilan fosthiazat, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, hydramethylnon, hydroprene, imidacloprid, iodfenfos, iprobenfos, isazophos, isoamidophos, isofenphos, isoprocarb, isoprothiolane, isoxathion, ivermectin, lama-cyhalothrin, lufenuron, kadedrin, lambda-cyhalothrin, lufenuron, malathion, mecarban-, mervinphos, mesulfenphos, n-etaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin, naled, NC 184, NI 125, nicotin, nitenpyram, omethoate, oxamyl, oxydemet hon M, oxydeprofos, parathion A, parathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozin, pyrachiophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, 15 quinaiphos, resmethrin, RHI-7988, rotenone, salithion, sebufos, silafluofen, sulfotep, suiprofos, tau-fluvalinate, tar oils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, tetramethrin, tetramethacarb, thiafenox, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazamnate, triazuron, trichiorfon, triflumuron, trimethacarb, vamidothion, XMvC, xylylcarb, zetamethrin; Molluscicides such as: fentin acetate, metaldehyde, methiocarb. niclosaniide; Herbicides and further algicides such as: acetochior, acifluorfen, aclonifen, acrolein, alachior, alloxydim, ametryn, amidosulfuron, amitrole, ammonium suiphamate, anilofos, asulam, atrazine, aziptrotryne, azimsulfuron, benazolin, benfluralin, benfuresate, bensulfuron, bensulfide, bentazone, benzofencap, benzthiazuron, bifenox, borax, bromacil, bromobutide, bromofenoxim, bromoxynil, butachior, butamifos, butralin, butylate, bialaphos, benzoyl-prop, bromobutide, carbetamide, chiomethoxyfen, chioramben, chlorbromuron, chiorfiurenol, chioridazon, chiorimuron, chiomnitrofen, chioroacetic acid, chiorotoluron, chioroxuron, chiorpropham, chiorsulfuron, chiorthal, chiorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, chiomeprop, clopyralid, cyanamide, cyanazine, cycloate, cycloxydim, chioroxynil, clodinafop-propargyl, cumnyluron, CGA 248757, clometoxyfen, cyhalofop, clopyrasuluron, cyclosulfamuron, 16 dichiorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachior, dimethipin, dinitramine, dinoseb, dinoseb acetate, dinoterb, diphenamnid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichiobenil, dimethamid, dithiopyr, dimethametryn, eglinazine, endothal, EPTC, esprocarb, ethalfiuralin, ethidimuron, ethofumesate, ethobenzanid, ethoxyfen, ET 751, ethametsulfuiron, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fuenachior, fluchioralin, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate, flurenol, flurochioridone, fluroxypyr, fomesafen, fosamine, flampropisopropyl, flamprop-isopropyl-L, flurniclorac-pentyl, flumipropyn, flumioxzim, flurtatone, flumioxzim, glyphosate, glufosinate-ammonium, haloxyfop, hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, imazosulfuron, KIJH 911, KUH 920, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachior, methabenzthiazuron, methazole, methoroptryne, methyldymron, methylisothiocyanates, metobromuron, metoxuron, metribuzin, metsulfuron, molinate, monalide, monolinuron, MSMA, metolachior, metosulam, 44'N metobenzuron, -17naproanilide, napropamide, naptalam, neburon, nicosulfuron, norfiurazon, oxadiazon, oxyfluorfen, orbencarb, oryzalin, quinchiorac, quinmerac, propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachiorophenol, pentanochior, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, prometryn, propachlor, propanil, propaquizafob, propazine, propham, pyrithiobac, quinmerac, quinocloamine, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, sifuron, simazine, simetryn, sodium chlorate, sulfometuron, sulfentrazone, sulcotrione, sulfosate, tar oils, TCA, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin, thiazopyr, triflusulfuron, vernolate.

The proportions by weight of the active substances in these active-substance combinations can be varied within relatively wide ranges.

Preferably, the active-substance combinations receive the benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin in proportions of from 0.1 to 99.9%, in particular from 1 to 75% and, with particular preference, from 5 to -18the remainder to 100% being made up by one or more of the abovementioned cocomponents.

A concentrate which can be used to protect emulsion paints, antifouling paints and other industrial materials against algae contain the active substances of the invention, or the active-substance combination, in a concentration of from 0.01 to 95% by weight, in particular from 0.1 to 60% by weight.

The use concentrations of the materials or of the active-substance combinations depends on the nature and the incidence of the algae to be controlled and on the composition of the paint to be protected. The optimum amount for use can be determined by means of test series. In general, the use concentrations lie within the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the paint to be protected.

The following examples are intended to illustrate the possibility of use of the active substances as algicides: -19- Examples Example I 0.5% of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are each incorporated into an exterior emulsion paint based on styrene acrylate.

Subsequently, the coating materials containing active substances are painted onto cardboard, on both sides.

The test specimens are contaminated by dipping them into an algal suspension comprising Phormidium, Oscillatoria, Chlorella and Scenedesmus species and are placed in Petri dishes filled with Allen's agar and inoculated with the aforementioned algae.

After 4 weeks of incubation at room temperature and 1200-1500 LUX, the plates containing benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin showed very good algal resistance, whereas a control, free of active substance, is completely infested by test organisms.

Example II of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are each incorporated into an exterior emulsion paint based on styrene acrylate.

Subsequently, the coating materials containing active substances are painted onto cardboard, on both sides.

The test specimens are subsequently leached for 24 h at a flow rate of 12 1/h and at 0

C.

After the end of the irrigation cycle, the samples are removed from the water, rinsed off and dried for 24 h.

The test specimens are contaminated by dipping them into an algal suspension comprising Phormidium, Oscillatoria, Chlorella and Scenedesmus species and are placed in Petri dishes filled with Allen's agar and inoculated with the aforementioned algae.

After 4 weeks of incubation at room temperature and 1200-1500 LUX, the plates containing benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin show very good algal resistance, whereas a control, free of active substance, was completely infested by test organisms.

In analogy to Example I and II, the experiments are conducted with polyvinyl acetatebased exterior emulsion paint.

In this cise, no infestation is found with 0.5% of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin, with and without irrigation, whereas the untreated controls are completely infested.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken :e :o as, an acknowledgement or any orrm of suggestion that the prior art forms part of athe common general knowledge in Australia.

9 g

Claims (4)

1. A method for controlling algal growth on industrial materials comprising admixing or treating said industrial materials with a mixture of at least two compounds selected from the group consisting of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon, and ethiozin, wherein the industrial materials are selected from the group consisting of interior emulsion paints, exterior emulsion paints, antifouling paints, wood preservative paints, stains, varnishes, polymer coatings, latices, adhesives, glues and textiles.

2. A composition comprising an industrial material containing a mixture of at least two components selected from the group consisting of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon, and ethiozin in an admixture with at least one active substance that provides a synergistic complement for the 15 control of algae, wherein the industrial material is selected from the group 0 consisting of interior emulsion paints, exterior emulsion paints, antifouling paints, wood preservative paints, stains, varnishes, polymer coatings, latices, adhesives, glues and textiles. SOVO 0 20

3. A composition according to claim 2, additionally comprising at least one component selected from the group consisting of fungicide, bactericide, molluscicide, insecticide, herbicide, algicide, and antifouling active substances. 0

4. Methods for controlling algal growth on industrial materials, substantially as 25 hereinbefore described with reference to the Examples. o000 00 Compositions comprising an industrial material, substantially as hereinbefore described with reference to the Examples. DATED this 24th day of May, 2001 BAYER AKTIENGESELLSCHAFT By its Patent Attorneys DAVIES COLLISON CAVE