CA2289724A1 - Algicides - Google Patents
Algicides Download PDFInfo
- Publication number
- CA2289724A1 CA2289724A1 CA002289724A CA2289724A CA2289724A1 CA 2289724 A1 CA2289724 A1 CA 2289724A1 CA 002289724 A CA002289724 A CA 002289724A CA 2289724 A CA2289724 A CA 2289724A CA 2289724 A1 CA2289724 A1 CA 2289724A1
- Authority
- CA
- Canada
- Prior art keywords
- tebuthiuron
- isoproturon
- ethiozin
- benzthiazuron
- methabenzthiazuron
- 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.)
- Abandoned
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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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G1/00—Cocoa; Cocoa products, e.g. chocolate; Substitutes therefor
- A23G1/04—Apparatus specially adapted for manufacture or treatment of cocoa or cocoa products
- A23G1/042—Manufacture or treatment of liquid, cream, paste, granule, shred or powder
- A23G1/047—Transformation of liquid, paste, cream, lump, powder, granule or shred into powder, granule or shred; Manufacture or treatment of powder
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
- A23L7/10—Cereal-derived products
- A23L7/109—Types of pasta, e.g. macaroni or noodles
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Nutrition Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to novel applications of known active substances such as benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin, in addition to mixtures containing other know active substances, to control the growth of algae on paints, antifouling paints and other technical materials.
Description
Le A 32 411-Foreyyn Countries Lin/li/bo/W6 / V04.02.1998 Al~icides FILk, Pty THIS ~~
~H~,l~Sln~~ll~
The present invention relates to the novel use of the known active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin and their mixtures, and mixtures of these active substances with other known active substances, for the control of algal infestation of architectural paints, antifouling paints and other industrial materials.
O
ni ~NHCH3 C, I W
'' H
E3enzthiazuron O
~NHCH3 / \
C, I :>~-N\
INethabenzthiazuron O
HsC CHs ,S
H3C N.-I~ ~ NHCH3 Tebuthiuron Le A 32 411-Forei n Countries O
/.
HsC I H N
\. CH3 Isoproturon H3C CHs O
NHZ
HsC ~ N/
N
N SC2Hs E=thiozin It has already been disclosed that broad-leaved weeds can be controlled selectively with benzthiazuron and methabenzthiazuron (cf. e.g. BE Patent 687 019;
US 2 756 135; G13 1 085 X130).
It is also known that broad-leaved weeds can be controlled with tebuthiuron (cf.
DE 1 816 568) an,d ethiozin (cf. US 3 671 523).
Isoproturon is likewise employed to control unwanted broad-leaved weed growth (see e.g. DE 2 03!~ 041).
Furthermore, in t'~he coursf: of studies of the environmental behaviour of isoproturon, the activity with respect to some freshwater algae has been disclosed (see M. Manthey et a:l., Sci. Total Environ. 1993, pp. 453-459; F.A. Anton et al., Sci.
Total Environ. 1993, pp. 845-851; J.LN. Kumar, J. Indian Bot. Soc. 70, 277 (1991)).
It has now une;cpectedly been found that the active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are also suitable for the Le A 32 411-Foreign Countries control of algal infestation of architectural paints, antifouling paints and other industrial materials. Thiis 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 additionalhr 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 eflFect. 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. vi combination with fungicides, there is a synergistic increase in the level of action in this case.
It has additionall:~ been found that the action of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon ;end ethiozin can also be improved considerably, in some cases even synergistically., by mixing in further herbicides, algicides and/or material-protectants as co-compone;nts.
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 Hormog~oneae.
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 Chamaesiphonalea and Pleurocapsales, of species of the genera Chamaesiphon and Dermatocarpa; fi~om the order of the Oscillatoriales, of species of the genera Phormidium, Sch.izothrix, Spirulina, Plectonema and Lyngbya; from the order of the Nostocales, of s~?ecies o:f the genera Nostoc, Rivularia, Tolypothrix, Scytonema, Le A 32 411-Foreiyntries 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 i'rom the: divisions Heterokontophyta, Rhodophyta, Chlorophyta, Euglenophyta, Cryptoph5rta, Dinophyta and Haptophyta. By way of example - but 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 Chrysophyc:eae, 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, P'adina, Dictyopteris, Laminaria, Macrocystis, Lessonia, Nerocystis, Chorda, Alaria, Fucus, Ascophyllum, Himanthalia, Sargassum, Cystoseira, Halidrys, Pelvetia, Coccophora and Durvilla; from the class of the Rho-dophyceae (red algae), of species of the genera Porphyridum, Bangia, Porphyra, Corallina, Lithothamnia, Lithophyllum, Rhodymania, Delesseria, Grinnellia, Platy-siphonia, 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, Apatococcus, I>esmococ:cus, Cladophora, Siphonocladus, Valonia, Caulerpa, Bryopsis, Acetabularia, Halimeda and Tuna.
The industrial materials or media to be given an a.lgicidal treatment preferably comprise wood preservative paints, stains and varnishes, polymer coatings, latices, adhesives, glue and textiles, and especially interior and exterior emulsion paints and antifouling paint;.
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.
Le A 32 411-Foreign Countries 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.
S
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 19'73.
Examples of acknowledged binders in antifouling paints are polyvinyl chloride in a solvent system, ~~hlorinat~ed rubber in a solvent system, acrylic resins in a solvent system especially in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the foam 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, isoF~roturon and/or ethiozin are incorporated either directly or as a formulation/mixture into the abovementioned antifouling paints or into the starting materials for thf;m. Ben:zthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin can also lie incorporated into self-polishing antifouling systems, as, for example, into the combinations mentioned below.
Le A 32 411-Foreign Countries For their in<:orporation into the industrial materials, benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are preferably in the form of 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 sub;>tances with extenders: that is, liquid solvents, pressurized liquefied gases md/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 m extender it is also possible, for example, to use organic solvents as auxiliary solvents. Suitabile liquid solvents are essentially aromatics, such as xylene, toluene, alkyln~~phthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as <:hlorobenzenes, 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; suitat>le solid carriers are, for example, natural ground minerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous eaJ h 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, Le A 32 411-Foreign Countries arylsulphonates, and also protein hydrolysates; suitable dispersants are, for example, lignin-sulphite w~~ste 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 axe mineral and vegel:able oils.
It is possible to use colorants such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian F3lue, andl 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.
1 S The present invention additionally provides synergistically acting mixtures of benzthiazuron, m~ethabenzthiazuron, 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 substancca 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:
Le A 32 411-Foreign Countries _g_ Triazoles such ass:
azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, dinico:nazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, l:enethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazol, pe;nconazole, propioconazole, (~-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptancd, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, tri-flumizole, triticonazole, uniconazole and their metal salts and acid adducts;
Imidazoles such as:
clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar, 1-imidazolyl--1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one and their metal salts and acid adducts;
Pyridines and p;yrimidines such as:
ancymidol, buthi~obate, fenarimol, nuarimol, triamirol;
Succinate dehydlrogenase inhibitors such as:
benodanil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, fur-carbanil, furmec~~clox, mebenil, mepronil, methfuroxam, metsulfovax, pyrocarbolid, oxycarboxin, Shirlan, Seedvax;
Naphthalene derivatives such as:
terbinafine, naftilnne, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);
Sulphenamides such as:
dichlorfluanid, todylfluanid, folpet, fluorfolpet; captan, captofol;
Ix A 32 411-Foreign Countries Benzimidazoles such as:
carbendazim, benomyl, fuberidazole, thiabendazole or salts thereof;
Morpholine deriivates such as:
S aldimorph, dime;thomorph, dodemorph, falimorph, fenpropidin fenpropimorph, tridemorph, trim~orphamide and their salts with arylsulphonic acids, such as e.g.
p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid;
Benzothiazoles 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 :~s:
boric acid, borates, borax;
Formaldehyde and formaldehyde donor compounds such as:
benzyl alcohol mono-(poly)-hemiformal, n-butanol hemiformal, dazomet, ethylene glycol hemiform~al, hexa-hydro-S-triazines, hexamethylenetetramine, N-hydroxy-methyl-N'-methylthiourea, N-methylolchloroacetamide, oxazolidines, para-formaldehyde, tauroline:, tetrahydro-1,3-oxazine, N-(2-hydroxypropyl)-amine-methanol;
Isothiazolinones such as:
N-methylisothiaz~olin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5~-chloro-N-octylisothiazolinone, N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones;
Le A 32 411-Foreign Countries Aldehydes such as:
cinnamaldehyde, formaldehyde, glutardialdehyde, ~3-bromocinnamaldehyde;
Thiocyanates such as:
thiocyanatometh~~lthioben.zothiazole, methylenebisthiocyanate;
Quaternary ammonium compounds such as:
benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldi-methyldodecylanlmoniurn chloride, dichlorobenzyl-dimethyl-alkyl-ammonium-chloride, didecyl~3imethylammonium chloride, dioctyl-dimethyl-ammonium chloride, N-hexadecyl-trimethyl-ammonium chloride, 1-hexadecyl-pyridinium chloride;
Iodine derivates such as:
diiodomethyl-p-t~~lyl sulplhone, 3-iodo-2-propinyl-alcohol, 4-chlorophenyl-3-iodopro-pargyl 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-butylcarba-mate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenyk;arbamate;
Phenols such as:
tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chloro-phenol, phenoxyethanol, dichlorophen, 2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-di-chlorophenoxy)-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-t~romo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-aceto-phenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazoldinones, (3-bromo-(3-nitro-styrene, chloroacetamide, chloramine T, 1,3-dibromo-4,4,5,5-tetrametyl-2-imidazol-Le A 32 411-Forei n Countries dinones, dichlora~mine T, 3,4-dichloro-(3H)-1,2-dithiol-3-one, 2,2-dibromo-3-nitril-propionamide, 1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid, phenyl 2-chlorocyanovinyl sulphone, phenyl 1,2-dichloro-2-cyanovinyl sulphone, tri-chloroisocyanuric: acid;
Pyridines such as:
1-hydroxy-2-pyriiiinethione (and the Na, Fe, Mn, Zn salts thereof), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-t~~imethylpentyl)-2( 1 H)-pyridine;
MethoxyacrylatES or the like such as:
methyl (E)-metho~ximino[alpha-(o-tolyloxy)-o-tolyl]acetate, (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide, (E)-2- { 2-[6-(2-cy anophenoxy)pyrimidin-4-yloxy]phenyl }-3-methoxyacrylate, O-methyl-2-[([3-methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximinoacetimi-date, 2-[[[[ 1-(2,5-dimes:hylphenyl)ethylidene]amino]oxy]methyl]-.alpha.-(methoximino)-N-metyl-benzene;~cetamide, alpha-(methoxyinuno)-N-methyl-2-[[[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-benzeneacetamide, alpha-(methoxyimino)-2-[ [[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-1>enzeneacetic acid methyl ester, alpha-(methoxymethylene;)-2-[[[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-benzeneacetic acid methyl ester, 2-[[[5-chloro-3-(t~rifluormeahyl)-2-pyridinyl]oxy]methyl]-.alpha.-(methoxyimino)-N-methyl-benzeneac:etamide, 2-[[[cyclopropyl[1;4-ethoxyphenyl)imino]methyl]thio]methyl]-.alpha.-(methoxyimino)-benzeneacetic acid methyl ester, alpha-(methoxyinlino)-N-methyl-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneacetamide, Le A 32 411-Foreign Countries alpha-(methoxyrnethylene)-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneace;tic acid methyl ester, alpha-(methoxyi mino)-N--methyl-2-[[ [ 1-[3-(trifluoromethyl)phenyl]-ethoxy]imino]mcahyl]-be:nzeneacetamide, 2-[[(3,5-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-1-yl]-.alpha.-(methoxymethylene)-ben:aeneacetic acid methyl ester;
Metal soaps such as:
the naphthenates, octoates, 2-ethylhexanoates, 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, Cu20, C;uO, ZnO;
Dithiocarbamates such :~s:
cufraneb, ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, Na or K
dimethyldithiocarbamate, macozeb, maneb, metam, metiram, thiram, zineb, ziram;
Nitrites such as:
2,4,5,6-tetrachloroisophth.alodinitrile, disodium cyano-dithioimidocarbamate;
Quinolines such as:
8-hydroxyquinoline and ita Cu salts;
Le A 32 411-Fonei~.ntries Other fungicides and bactericides such as:
5-hydroxy-2(SH)-furanone; 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, N-(2-p-chlorobenzoylethy~l)-hexaminium chloride, 2-oxo-2-(4-hydroxy-phenyl)acet-hydroximic chloride, tr-is-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(cyclo-hexyl-diazeniumdioxy)-tributyltin and K salts, bis-N-(cyclohexyldiazeniumdioxy)-copper;
Ag, Zn or Cu-containing zeolites alone or enclosed in polymeric materials Insecticides / ac:~ricides ,/ nematicides such as:
abamectin, acephat, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, alpha-~cyperzne.thrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azin~~hos M, :azocyclotin, Bacillus thuringiensis, ba.rthr~in, 4-bromo-2(4-chlorophenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-11-1-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacy-fluthrin, bifenthrin, bioresmethrin, bioallethrin, bromophos A, bromophos M, bufencarb, buprofezin, butathiophos, butocarboxin, butoxycarboxim, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chino-methionat, cloethocarb, chlordane, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methylJ-N'-cyano-N-methyl-ethanimid-amide, chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, cypophenothrin clofentezin, coumaphos, cyanophos, cycloprothr~in, cyfluthrin, cyhalothrin, cyhe.xatin, cypermethrin, cyromazin, decamethrin, de:ltamethrin, demeton M, demeton S, demeton-S-methyl, dia-fenthiuron, 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-phe;noxybenzyl ether, dimethylvinphos, dioxathion, disulfoton, Le A 32 411-Forei n Countries eflusilanate, em~unectin, empenthrin, endosulfan, EPN, esfenvalerat, ethiofencarb, ethion, ethofenprox, etrirr~phos, 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, iso-procarb, isoprothiolane, is,oxathion, ivermectin, lama-cyhalothrin, lufenuron, kadedrin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin, naled, NC 184, T'I 125, nicotin, nitenpyram, omethoate, oxamyl, oxyde;methon M, oxydeprofos, parathion A, p~~rathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, ~phenthoa.te, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirinniphos 1VI, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphen-thion, pyresmetln~in, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, Ix A 32 411-Forei n Countries quinalphos, resmethrin, RH-T988, rotenone, salithion, sebufo~~, silafluofen, sulfotep, sulprofos, tau-fluvalinate, tar oils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, teme;phos, te:rbam, terbufos, tetrachlorvinphos, tetramethrin, tetra-methacarb, thiafenox, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazamate, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XN(C, xylylcarb, zetamethrin;
Molluscicides such as:
fentin acetate, me;taldehyd.e, methiocarb. niclosamide;
Herbicides and further algicides such as:
acetochlor, acifluorfen, a~clonifen, acrolein, alachlor, alloxydim, ametryn, amido-sulfuron, amitrole, ammonium sulphamate, anilofos, asulam, atrazine, aziptrotryne, azimsulfuron, benazolin, benfluralin, benfuresate, bensulfuron, bensulflde, bentazone, benzofencap, benzthiazuron, biifenox, borax, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butami.fos, butralin, butylate, bialaphos, benzoyl-prop, bromobutide, carbetamide, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, chlorotoluron, chloroxuron, chl.orpropham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, cle~:hodim, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, Le A 32 411-For~:i n Countries cycloate, cyclox5~dim, chl.oroxynil, clodinafop-propargyl, cumyluron, CGA
248757, clometoxyfen, cyhalofop, clopyrasuluron, cyclosulfamuron, dichlorprop, diclhlorprop--P, diclofop, diethatyl, difenoxuron, difenzoquat, diflu-fenican, dimefur~on, dime;piperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb acetate, dinoterib, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicarnba, dichlobenil, dimethamid, dithiopyr, dimethametryn, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, ethobenzanid, ethoxyfen, ET 751, ethametsulfuron, fenoxaprop, fenoxaprop-F', fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fuenachlor, fluchloralin, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate, flunenol, flurochloridone, fluroxypyr, fomesafen, fosamine, flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl, flumipropyn, flumioxzim, flurtatone, flumioxzim, glyphosate, glufosinate-annmonium, haloxyfop, hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, ima-zethapyr, ioxynil" isoprop;~lin, imazosulfuron, KUH 911, KUH '~20, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-t:hioethyl" MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazuron, methazole, methoroptryne, Le A 32 411-Foreign Countries methyldymron, methylisothiocyanates, metobromuron, metoxuron, metribuzin, metsulfuron, molinate, lnonalide, monolinuron, MSMA, metolachlor, metosulam, metobenzuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oxadiazon, oxyfluorfen, orbencarb, oryzalin, quinchlorac, quinmerac, propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, prornetryn, yropachlor, propanil, propaquizafob, propazine, propham, pyrithiobac, quinmerac, quinocloamine, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, sifuron, s,imazine, simetryn, sodium chlorate, sulfometuron, sulfentrazone, sulcotrione, sulfosate, tar oils, TCA, tebutam, te:buthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin, thiazopyr, triflusu~lfuron, vernolate.
The proportions by weight of the active substances in these active-substance combinations can be varied within relatively wide ranges.
Le A 32 411-Foreign Countries Preferably, the active-substance combinations receive the benzthiazuron, methabenz-thiazuron, 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 SO%, the remainder to 100% being made up by one or more of the abovementioned co-components.
A concentrate which can be used to protect emulsion paints, antifouling paints and other industrial rr~aterials against algae contain the active substances of the invention, or the active-suh~stance 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 t:he 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% b:y weight, preferably from 0.05 to 1.0% by weight, based on the paint to be protected.
The following examples ~u-e intended to illustrate the possibility of use of the active substances as algi,cides:
Le A 32 411-Foreign Countries Examples Example I
0.5% of benzthiazuron, rnethabenzthiazuron, 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 bo~;h 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 o:f 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
0.5% of benzthi~~zuron, rnethabenzthiazuron, tebuthiuron, isoproturon and ethiozin are each incorporated unto an exterior emulsion paint based on styrene acrylate.
Subsequently, th~~ 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 20°C.
After the end of ~:he irrigation cycle, the samples are removed from the water, rinsed off and dried for :24 h.
Le A 32 411-Foreign Countries 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 acetate-based exterior emulsion paint.
In this case, no infestation. is found with 0.5% of benzthiazuron, methabenzthiazuron, tebuthiuron, isohroturon and ethiozin, with and without irrigation, whereas the untreated control; are completely infested.
~H~,l~Sln~~ll~
The present invention relates to the novel use of the known active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin and their mixtures, and mixtures of these active substances with other known active substances, for the control of algal infestation of architectural paints, antifouling paints and other industrial materials.
O
ni ~NHCH3 C, I W
'' H
E3enzthiazuron O
~NHCH3 / \
C, I :>~-N\
INethabenzthiazuron O
HsC CHs ,S
H3C N.-I~ ~ NHCH3 Tebuthiuron Le A 32 411-Forei n Countries O
/.
HsC I H N
\. CH3 Isoproturon H3C CHs O
NHZ
HsC ~ N/
N
N SC2Hs E=thiozin It has already been disclosed that broad-leaved weeds can be controlled selectively with benzthiazuron and methabenzthiazuron (cf. e.g. BE Patent 687 019;
US 2 756 135; G13 1 085 X130).
It is also known that broad-leaved weeds can be controlled with tebuthiuron (cf.
DE 1 816 568) an,d ethiozin (cf. US 3 671 523).
Isoproturon is likewise employed to control unwanted broad-leaved weed growth (see e.g. DE 2 03!~ 041).
Furthermore, in t'~he coursf: of studies of the environmental behaviour of isoproturon, the activity with respect to some freshwater algae has been disclosed (see M. Manthey et a:l., Sci. Total Environ. 1993, pp. 453-459; F.A. Anton et al., Sci.
Total Environ. 1993, pp. 845-851; J.LN. Kumar, J. Indian Bot. Soc. 70, 277 (1991)).
It has now une;cpectedly been found that the active substances benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are also suitable for the Le A 32 411-Foreign Countries control of algal infestation of architectural paints, antifouling paints and other industrial materials. Thiis 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 additionalhr 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 eflFect. 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. vi combination with fungicides, there is a synergistic increase in the level of action in this case.
It has additionall:~ been found that the action of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon ;end ethiozin can also be improved considerably, in some cases even synergistically., by mixing in further herbicides, algicides and/or material-protectants as co-compone;nts.
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 Hormog~oneae.
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 Chamaesiphonalea and Pleurocapsales, of species of the genera Chamaesiphon and Dermatocarpa; fi~om the order of the Oscillatoriales, of species of the genera Phormidium, Sch.izothrix, Spirulina, Plectonema and Lyngbya; from the order of the Nostocales, of s~?ecies o:f the genera Nostoc, Rivularia, Tolypothrix, Scytonema, Le A 32 411-Foreiyntries 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 i'rom the: divisions Heterokontophyta, Rhodophyta, Chlorophyta, Euglenophyta, Cryptoph5rta, Dinophyta and Haptophyta. By way of example - but 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 Chrysophyc:eae, 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, P'adina, Dictyopteris, Laminaria, Macrocystis, Lessonia, Nerocystis, Chorda, Alaria, Fucus, Ascophyllum, Himanthalia, Sargassum, Cystoseira, Halidrys, Pelvetia, Coccophora and Durvilla; from the class of the Rho-dophyceae (red algae), of species of the genera Porphyridum, Bangia, Porphyra, Corallina, Lithothamnia, Lithophyllum, Rhodymania, Delesseria, Grinnellia, Platy-siphonia, 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, Apatococcus, I>esmococ:cus, Cladophora, Siphonocladus, Valonia, Caulerpa, Bryopsis, Acetabularia, Halimeda and Tuna.
The industrial materials or media to be given an a.lgicidal treatment preferably comprise wood preservative paints, stains and varnishes, polymer coatings, latices, adhesives, glue and textiles, and especially interior and exterior emulsion paints and antifouling paint;.
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.
Le A 32 411-Foreign Countries 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.
S
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 19'73.
Examples of acknowledged binders in antifouling paints are polyvinyl chloride in a solvent system, ~~hlorinat~ed rubber in a solvent system, acrylic resins in a solvent system especially in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the foam 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, isoF~roturon and/or ethiozin are incorporated either directly or as a formulation/mixture into the abovementioned antifouling paints or into the starting materials for thf;m. Ben:zthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin can also lie incorporated into self-polishing antifouling systems, as, for example, into the combinations mentioned below.
Le A 32 411-Foreign Countries For their in<:orporation into the industrial materials, benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and ethiozin are preferably in the form of 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 sub;>tances with extenders: that is, liquid solvents, pressurized liquefied gases md/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 m extender it is also possible, for example, to use organic solvents as auxiliary solvents. Suitabile liquid solvents are essentially aromatics, such as xylene, toluene, alkyln~~phthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as <:hlorobenzenes, 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; suitat>le solid carriers are, for example, natural ground minerals, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous eaJ h 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, Le A 32 411-Foreign Countries arylsulphonates, and also protein hydrolysates; suitable dispersants are, for example, lignin-sulphite w~~ste 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 axe mineral and vegel:able oils.
It is possible to use colorants such as inorganic pigments, e.g. iron oxide, titanium oxide, Prussian F3lue, andl 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.
1 S The present invention additionally provides synergistically acting mixtures of benzthiazuron, m~ethabenzthiazuron, 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 substancca 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:
Le A 32 411-Foreign Countries _g_ Triazoles such ass:
azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, dinico:nazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, l:enethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazol, pe;nconazole, propioconazole, (~-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptancd, 2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, tri-flumizole, triticonazole, uniconazole and their metal salts and acid adducts;
Imidazoles such as:
clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar, 1-imidazolyl--1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one and their metal salts and acid adducts;
Pyridines and p;yrimidines such as:
ancymidol, buthi~obate, fenarimol, nuarimol, triamirol;
Succinate dehydlrogenase inhibitors such as:
benodanil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, fur-carbanil, furmec~~clox, mebenil, mepronil, methfuroxam, metsulfovax, pyrocarbolid, oxycarboxin, Shirlan, Seedvax;
Naphthalene derivatives such as:
terbinafine, naftilnne, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);
Sulphenamides such as:
dichlorfluanid, todylfluanid, folpet, fluorfolpet; captan, captofol;
Ix A 32 411-Foreign Countries Benzimidazoles such as:
carbendazim, benomyl, fuberidazole, thiabendazole or salts thereof;
Morpholine deriivates such as:
S aldimorph, dime;thomorph, dodemorph, falimorph, fenpropidin fenpropimorph, tridemorph, trim~orphamide and their salts with arylsulphonic acids, such as e.g.
p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid;
Benzothiazoles 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 :~s:
boric acid, borates, borax;
Formaldehyde and formaldehyde donor compounds such as:
benzyl alcohol mono-(poly)-hemiformal, n-butanol hemiformal, dazomet, ethylene glycol hemiform~al, hexa-hydro-S-triazines, hexamethylenetetramine, N-hydroxy-methyl-N'-methylthiourea, N-methylolchloroacetamide, oxazolidines, para-formaldehyde, tauroline:, tetrahydro-1,3-oxazine, N-(2-hydroxypropyl)-amine-methanol;
Isothiazolinones such as:
N-methylisothiaz~olin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, 5~-chloro-N-octylisothiazolinone, N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones;
Le A 32 411-Foreign Countries Aldehydes such as:
cinnamaldehyde, formaldehyde, glutardialdehyde, ~3-bromocinnamaldehyde;
Thiocyanates such as:
thiocyanatometh~~lthioben.zothiazole, methylenebisthiocyanate;
Quaternary ammonium compounds such as:
benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldi-methyldodecylanlmoniurn chloride, dichlorobenzyl-dimethyl-alkyl-ammonium-chloride, didecyl~3imethylammonium chloride, dioctyl-dimethyl-ammonium chloride, N-hexadecyl-trimethyl-ammonium chloride, 1-hexadecyl-pyridinium chloride;
Iodine derivates such as:
diiodomethyl-p-t~~lyl sulplhone, 3-iodo-2-propinyl-alcohol, 4-chlorophenyl-3-iodopro-pargyl 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-butylcarba-mate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenyk;arbamate;
Phenols such as:
tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chloro-phenol, phenoxyethanol, dichlorophen, 2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-di-chlorophenoxy)-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-t~romo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-aceto-phenone, 1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazoldinones, (3-bromo-(3-nitro-styrene, chloroacetamide, chloramine T, 1,3-dibromo-4,4,5,5-tetrametyl-2-imidazol-Le A 32 411-Forei n Countries dinones, dichlora~mine T, 3,4-dichloro-(3H)-1,2-dithiol-3-one, 2,2-dibromo-3-nitril-propionamide, 1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid, phenyl 2-chlorocyanovinyl sulphone, phenyl 1,2-dichloro-2-cyanovinyl sulphone, tri-chloroisocyanuric: acid;
Pyridines such as:
1-hydroxy-2-pyriiiinethione (and the Na, Fe, Mn, Zn salts thereof), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-t~~imethylpentyl)-2( 1 H)-pyridine;
MethoxyacrylatES or the like such as:
methyl (E)-metho~ximino[alpha-(o-tolyloxy)-o-tolyl]acetate, (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide, (E)-2- { 2-[6-(2-cy anophenoxy)pyrimidin-4-yloxy]phenyl }-3-methoxyacrylate, O-methyl-2-[([3-methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximinoacetimi-date, 2-[[[[ 1-(2,5-dimes:hylphenyl)ethylidene]amino]oxy]methyl]-.alpha.-(methoximino)-N-metyl-benzene;~cetamide, alpha-(methoxyinuno)-N-methyl-2-[[[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-benzeneacetamide, alpha-(methoxyimino)-2-[ [[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-1>enzeneacetic acid methyl ester, alpha-(methoxymethylene;)-2-[[[[ 1-[3-(trifluoromethyl)phenyl]ethyli-dene]amino]oxy]methyl]-benzeneacetic acid methyl ester, 2-[[[5-chloro-3-(t~rifluormeahyl)-2-pyridinyl]oxy]methyl]-.alpha.-(methoxyimino)-N-methyl-benzeneac:etamide, 2-[[[cyclopropyl[1;4-ethoxyphenyl)imino]methyl]thio]methyl]-.alpha.-(methoxyimino)-benzeneacetic acid methyl ester, alpha-(methoxyinlino)-N-methyl-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneacetamide, Le A 32 411-Foreign Countries alpha-(methoxyrnethylene)-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneace;tic acid methyl ester, alpha-(methoxyi mino)-N--methyl-2-[[ [ 1-[3-(trifluoromethyl)phenyl]-ethoxy]imino]mcahyl]-be:nzeneacetamide, 2-[[(3,5-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-1-yl]-.alpha.-(methoxymethylene)-ben:aeneacetic acid methyl ester;
Metal soaps such as:
the naphthenates, octoates, 2-ethylhexanoates, 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, Cu20, C;uO, ZnO;
Dithiocarbamates such :~s:
cufraneb, ferban, potassium N-hydroxymethyl-N'-methyl-dithiobarbamate, Na or K
dimethyldithiocarbamate, macozeb, maneb, metam, metiram, thiram, zineb, ziram;
Nitrites such as:
2,4,5,6-tetrachloroisophth.alodinitrile, disodium cyano-dithioimidocarbamate;
Quinolines such as:
8-hydroxyquinoline and ita Cu salts;
Le A 32 411-Fonei~.ntries Other fungicides and bactericides such as:
5-hydroxy-2(SH)-furanone; 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone, N-(2-p-chlorobenzoylethy~l)-hexaminium chloride, 2-oxo-2-(4-hydroxy-phenyl)acet-hydroximic chloride, tr-is-N-(cyclohexyldiazeniumdioxy)-aluminium, N-(cyclo-hexyl-diazeniumdioxy)-tributyltin and K salts, bis-N-(cyclohexyldiazeniumdioxy)-copper;
Ag, Zn or Cu-containing zeolites alone or enclosed in polymeric materials Insecticides / ac:~ricides ,/ nematicides such as:
abamectin, acephat, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, alpha-~cyperzne.thrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azin~~hos M, :azocyclotin, Bacillus thuringiensis, ba.rthr~in, 4-bromo-2(4-chlorophenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-11-1-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacy-fluthrin, bifenthrin, bioresmethrin, bioallethrin, bromophos A, bromophos M, bufencarb, buprofezin, butathiophos, butocarboxin, butoxycarboxim, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chino-methionat, cloethocarb, chlordane, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methylJ-N'-cyano-N-methyl-ethanimid-amide, chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, cypophenothrin clofentezin, coumaphos, cyanophos, cycloprothr~in, cyfluthrin, cyhalothrin, cyhe.xatin, cypermethrin, cyromazin, decamethrin, de:ltamethrin, demeton M, demeton S, demeton-S-methyl, dia-fenthiuron, 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-phe;noxybenzyl ether, dimethylvinphos, dioxathion, disulfoton, Le A 32 411-Forei n Countries eflusilanate, em~unectin, empenthrin, endosulfan, EPN, esfenvalerat, ethiofencarb, ethion, ethofenprox, etrirr~phos, 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, iso-procarb, isoprothiolane, is,oxathion, ivermectin, lama-cyhalothrin, lufenuron, kadedrin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metalcarb, milbemectin, monocrotophos, moxiectin, naled, NC 184, T'I 125, nicotin, nitenpyram, omethoate, oxamyl, oxyde;methon M, oxydeprofos, parathion A, p~~rathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, ~phenthoa.te, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirinniphos 1VI, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphen-thion, pyresmetln~in, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, Ix A 32 411-Forei n Countries quinalphos, resmethrin, RH-T988, rotenone, salithion, sebufo~~, silafluofen, sulfotep, sulprofos, tau-fluvalinate, tar oils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, teme;phos, te:rbam, terbufos, tetrachlorvinphos, tetramethrin, tetra-methacarb, thiafenox, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazamate, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XN(C, xylylcarb, zetamethrin;
Molluscicides such as:
fentin acetate, me;taldehyd.e, methiocarb. niclosamide;
Herbicides and further algicides such as:
acetochlor, acifluorfen, a~clonifen, acrolein, alachlor, alloxydim, ametryn, amido-sulfuron, amitrole, ammonium sulphamate, anilofos, asulam, atrazine, aziptrotryne, azimsulfuron, benazolin, benfluralin, benfuresate, bensulfuron, bensulflde, bentazone, benzofencap, benzthiazuron, biifenox, borax, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butami.fos, butralin, butylate, bialaphos, benzoyl-prop, bromobutide, carbetamide, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, chlorotoluron, chloroxuron, chl.orpropham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, cle~:hodim, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, Le A 32 411-For~:i n Countries cycloate, cyclox5~dim, chl.oroxynil, clodinafop-propargyl, cumyluron, CGA
248757, clometoxyfen, cyhalofop, clopyrasuluron, cyclosulfamuron, dichlorprop, diclhlorprop--P, diclofop, diethatyl, difenoxuron, difenzoquat, diflu-fenican, dimefur~on, dime;piperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb acetate, dinoterib, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicarnba, dichlobenil, dimethamid, dithiopyr, dimethametryn, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, ethobenzanid, ethoxyfen, ET 751, ethametsulfuron, fenoxaprop, fenoxaprop-F', fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fuenachlor, fluchloralin, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate, flunenol, flurochloridone, fluroxypyr, fomesafen, fosamine, flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl, flumipropyn, flumioxzim, flurtatone, flumioxzim, glyphosate, glufosinate-annmonium, haloxyfop, hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, ima-zethapyr, ioxynil" isoprop;~lin, imazosulfuron, KUH 911, KUH '~20, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-t:hioethyl" MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazuron, methazole, methoroptryne, Le A 32 411-Foreign Countries methyldymron, methylisothiocyanates, metobromuron, metoxuron, metribuzin, metsulfuron, molinate, lnonalide, monolinuron, MSMA, metolachlor, metosulam, metobenzuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oxadiazon, oxyfluorfen, orbencarb, oryzalin, quinchlorac, quinmerac, propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, prornetryn, yropachlor, propanil, propaquizafob, propazine, propham, pyrithiobac, quinmerac, quinocloamine, quizalofop, quizalofop-P, rimsulfuron, sethoxydim, sifuron, s,imazine, simetryn, sodium chlorate, sulfometuron, sulfentrazone, sulcotrione, sulfosate, tar oils, TCA, tebutam, te:buthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin, thiazopyr, triflusu~lfuron, vernolate.
The proportions by weight of the active substances in these active-substance combinations can be varied within relatively wide ranges.
Le A 32 411-Foreign Countries Preferably, the active-substance combinations receive the benzthiazuron, methabenz-thiazuron, 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 SO%, the remainder to 100% being made up by one or more of the abovementioned co-components.
A concentrate which can be used to protect emulsion paints, antifouling paints and other industrial rr~aterials against algae contain the active substances of the invention, or the active-suh~stance 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 t:he 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% b:y weight, preferably from 0.05 to 1.0% by weight, based on the paint to be protected.
The following examples ~u-e intended to illustrate the possibility of use of the active substances as algi,cides:
Le A 32 411-Foreign Countries Examples Example I
0.5% of benzthiazuron, rnethabenzthiazuron, 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 bo~;h 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 o:f 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
0.5% of benzthi~~zuron, rnethabenzthiazuron, tebuthiuron, isoproturon and ethiozin are each incorporated unto an exterior emulsion paint based on styrene acrylate.
Subsequently, th~~ 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 20°C.
After the end of ~:he irrigation cycle, the samples are removed from the water, rinsed off and dried for :24 h.
Le A 32 411-Foreign Countries 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 acetate-based exterior emulsion paint.
In this case, no infestation. is found with 0.5% of benzthiazuron, methabenzthiazuron, tebuthiuron, isohroturon and ethiozin, with and without irrigation, whereas the untreated control; are completely infested.
Claims (6)
1. Use of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin for controlling algal growth on industrial materials.
2. Use according to Claim 1, characterized in that industrial materials in question are interior and exterior emulsion paints, antifouling paints, wood preservative paints, stains and varnishes, polymer coatings, latices, adhesives, glue and textiles.
3. Method of controlling algal growth on industrial materials, characterized in that the materials are admixed or treated with benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin.
4. Industrial materials comprising benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin.
5. Industrial materials, according to Claim 3, additionally comprising at least one fungicide, bactericide, molluscicide, insecticide, herbicide, algicide and/or antifouling active substance.
6. Compositions and concentrates comprising, in addition to benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin, at least one active substance which constitutes a synergistic complement for the control of algae.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19720342.6 | 1997-05-15 | ||
| DE19720342A DE19720342A1 (en) | 1997-05-15 | 1997-05-15 | Use of benzthiazuron, methabenzthiazuron, tebuthiuron, isoproturon and/or ethiozin |
| PCT/EP1998/002617 WO1998051154A1 (en) | 1997-05-15 | 1998-05-04 | Algicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2289724A1 true CA2289724A1 (en) | 1998-11-19 |
Family
ID=7829521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002289724A Abandoned CA2289724A1 (en) | 1997-05-15 | 1998-05-04 | Algicides |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0982995B1 (en) |
| JP (1) | JP2001524976A (en) |
| KR (1) | KR20010012078A (en) |
| CN (1) | CN1283081A (en) |
| AU (1) | AU736095B2 (en) |
| BR (1) | BR9811464A (en) |
| CA (1) | CA2289724A1 (en) |
| DE (2) | DE19720342A1 (en) |
| DK (1) | DK0982995T3 (en) |
| ES (1) | ES2201500T3 (en) |
| MX (1) | MXPA99010092A (en) |
| NO (1) | NO323340B1 (en) |
| WO (1) | WO1998051154A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5469892B2 (en) * | 2008-03-25 | 2014-04-16 | 日本エンバイロケミカルズ株式会社 | Wood protective paint |
| DE202009004138U1 (en) | 2009-03-27 | 2009-06-04 | Lanxess Deutschland Gmbh | Algicide-protected plasters |
| EP2233003A1 (en) | 2009-03-27 | 2010-09-29 | LANXESS Deutschland GmbH | Algicide protected plaster |
| WO2011103124A1 (en) | 2010-02-17 | 2011-08-25 | Henry Company Llc | Microbe mitigating architectural barriers, compositions for forming such barriers and related methods |
| EP3010343B1 (en) * | 2013-08-30 | 2017-07-19 | Rohm and Haas Company | Synergistic combination of a lenacil compound and phenylurea herbicides for dry film protection |
| EP3087836B1 (en) * | 2015-04-28 | 2019-02-13 | Rotam Agrochem International Company Limited | Herbicidal composition and method for controlling plant growth |
| CN114668020B (en) * | 2020-12-24 | 2024-03-12 | 宁波三江益农化学有限公司 | Algae control composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8811948D0 (en) * | 1988-05-20 | 1988-06-22 | Ici Plc | Composition & use |
| DE4433856A1 (en) * | 1994-09-22 | 1996-03-28 | Bayer Ag | Antifouling agent for protecting objects in contact with water |
| AU3386195A (en) * | 1995-08-18 | 1997-03-12 | Bayer Aktiengesellschaft | Microbicidal formulations |
| DE19543097A1 (en) * | 1995-11-18 | 1997-05-22 | Riedel De Haen Ag | Algicide combination products for the preservation of technical materials |
-
1997
- 1997-05-15 DE DE19720342A patent/DE19720342A1/en not_active Withdrawn
-
1998
- 1998-05-04 DE DE59809348T patent/DE59809348D1/en not_active Expired - Lifetime
- 1998-05-04 DK DK98925526T patent/DK0982995T3/en active
- 1998-05-04 BR BR9811464-6A patent/BR9811464A/en not_active IP Right Cessation
- 1998-05-04 WO PCT/EP1998/002617 patent/WO1998051154A1/en active IP Right Grant
- 1998-05-04 CA CA002289724A patent/CA2289724A1/en not_active Abandoned
- 1998-05-04 ES ES98925526T patent/ES2201500T3/en not_active Expired - Lifetime
- 1998-05-04 EP EP98925526A patent/EP0982995B1/en not_active Expired - Lifetime
- 1998-05-04 CN CN98805075A patent/CN1283081A/en active Pending
- 1998-05-04 KR KR1019997009700A patent/KR20010012078A/en not_active Application Discontinuation
- 1998-05-04 JP JP54874898A patent/JP2001524976A/en active Pending
- 1998-05-04 MX MXPA99010092A patent/MXPA99010092A/en unknown
- 1998-05-04 AU AU77614/98A patent/AU736095B2/en not_active Ceased
-
1999
- 1999-11-10 NO NO19995492A patent/NO323340B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NO995492L (en) | 1999-11-10 |
| WO1998051154A8 (en) | 1999-12-09 |
| EP0982995A1 (en) | 2000-03-08 |
| MXPA99010092A (en) | 2003-07-21 |
| AU7761498A (en) | 1998-12-08 |
| AU736095B2 (en) | 2001-07-26 |
| WO1998051154A1 (en) | 1998-11-19 |
| KR20010012078A (en) | 2001-02-15 |
| DK0982995T3 (en) | 2003-12-01 |
| NO995492D0 (en) | 1999-11-10 |
| JP2001524976A (en) | 2001-12-04 |
| DE19720342A1 (en) | 1998-11-19 |
| BR9811464A (en) | 2000-09-12 |
| NO323340B1 (en) | 2007-04-02 |
| EP0982995B1 (en) | 2003-08-20 |
| DE59809348D1 (en) | 2003-09-25 |
| CN1283081A (en) | 2001-02-07 |
| ES2201500T3 (en) | 2004-03-16 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Dead |