Note: Descriptions are shown in the official language in which they were submitted.
CA 02289724 1999-11-12
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\
CH3
INethabenzthiazuron
O
HsC CHs
,S
H3C N.-I~ ~ NHCH3
CH3
Tebuthiuron
CA 02289724 1999-11-12
Le A 32 411-Forei n Countries
-2-
O
CH3
/CH3
/.
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
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-3-
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,
CA 02289724 1999-11-12
Le A 32 411-Foreiyntries
-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 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.
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-5-
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.
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-6-
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,
CA 02289724 1999-11-12
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:
CA 02289724 1999-11-12
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;
CA 02289724 1999-11-12
Ix A 32 411-Foreign Countries
-9-
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;
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
- 10-
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-
CA 02289724 1999-11-12
Le A 32 411-Forei n Countries
-11-
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,
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-12-
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;
CA 02289724 1999-11-12
Le A 32 411-Fonei~.ntries
- 13-
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,
CA 02289724 1999-11-12
Le A 32 411-Forei n Countries
- 14-
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,
CA 02289724 1999-11-12
Ix A 32 411-Forei n Countries
-15-
10
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,
CA 02289724 1999-11-12
Le A 32 411-For~:i n Countries
- 16-
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,
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-17-
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.
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-18-
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:
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
- 19-
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.
CA 02289724 1999-11-12
Le A 32 411-Foreign Countries
-20-
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.
