Note: Descriptions are shown in the official language in which they were submitted.
PF 70004 CA 02787550 2012-07-19
1
Anhydrous composition comprising a dissolved and a suspended pesticide, alkyl
lactate and alcohol
The present invention relates to an anhydrous formulation comprising a) a
first
pesticide in dissolved form, b) a second pesticide in the form of suspended
particles, c)
an alkyl lactate, and d) an alcohol. It further relates to a method of
controlling
phytopathogenic fungi and/or undesired plant growth and/or undesired insect or
mite
infestation and/or of regulating the growth of plants, where the specified
formulation is
allowed to act on the pests in question, their habitat or the plants to be
protected from
the particular pest, the soil and/or on undesired plants and/or the useful
plants and/or
their habitat. Furthermore, the invention relates to the use of the
formulation for
increasing the rain resistance of the applied pesticides. Combinations of
preferred
features with other preferred features are comprised by the present invention.
Agrochemical formulations should ideally have both a curative effect and also
a
preventative effect. Some of the known pesticides are particularly curatively
effective
whereas other pesticides are particularly preventatively effective. Thus, for
example,
boscalid has good preventative effectiveness when it is applied as suspended
particles
in a fine distribution over the leaf surface. Epoxiconazole is, for example,
particularly
curatively effective when it is applied as emulsion. In principle, it is
possible to prepare
mixtures of such pesticides as tank mixture directly in the spray tank from
the separate
formulations, for example from a suspension concentrate of boscalid and an
emulsion
concentrate of epoxiconazole. However, as experience shows, tank mixtures are
disadvantageous because different formulations have to be handled and their
mixing
ratios have to be adjusted. Often, a third pesticide should also additionally
be added,
for example to a mixture of curative and preventative fungicides, a herbicide,
insecticide or growth regulator should also be added. Here, the compatibility
of the
three formulations is very difficult to predict.
WO 2000/18227 discloses a nonaqueous suspension concentrate comprising 50 to
400 g/I of a crop protection agent, 50 to 700 g/I of an adjuvant and 75 to 500
g/I of a
solvent, such as alkyl lactates. Here, the suspension concentrate can comprise
a
mixture of active ingredients, where one of the active ingredients is
dissolved in the
continuous phase.
WO 2005/074685 discloses a composition for crop protection comprising 2-
ethylhexyl
lactate, agrochemical active ingredients dissolved therein and further
formulation
auxiliaries such as benzyl alcohol.
WO 2007/028538 discloses the use of alkyl lactates for improving the effect of
crop
protection agents, such as pyraclostrobin or epoxiconazole.
WO 2003/075657 discloses a liquid pesticide composition comprising one or more
CA 02787550 2012-07-19
PF 70004
2
pesticides as active ingredient and a lactate ester as crystallization
inhibitor. Suitable
pesticides are, for example, epoxiconazole or pyraclostrobin.
The formulations according to the prior art have various disadvantages:
suspension .
concentrates and emulsion concentrates have hitherto had to be mixed in the
tank by
the user himself. The formulations were not storage-stable or crystallized
out. The rain
resistance of the pesticides formulated in this way was low. The pesticides
were only
absorbed slowly or in small amounts into the leaf of the treated plant. The
pesticides
exhibit low effectiveness.
=
It was therefore an object of the present invention to find a formulation
comprising at
least two pesticides, where both a suspended and also a dissolved active
ingredient is
combined in a single formulation. The formulation should have high rain
resistance. It
should be absorbed very readily into the leaf surface. The formulation should
also be
storage-stable.
The object was achieved by an anhydrous formulation comprising
a) a first pesticide in dissolved form
b) a second pesticide in the form of suspended particles
c) an alkyl lactate, and
d) an alcohol.
Anhydrous formulations comprise in most cases at most 5% by weight of water,
preferably at most 1% by weight, particularly preferably at most 0.5% by
weight and in
particular at most 0.1% by weight.
The first pesticide is present in dissolved form. In most cases, at least 90%
by weight of
the first pesticide are dissolved, preferably at least 95% by weight and in
particular at
least 99% by weight. The first pesticide is generally dissolved in a
continuous phase of
the formulation.
The second pesticide is present in the form of suspended particles. In most
cases, at
least 90% by weight of the second pesticide are suspended, preferably at least
95% by
weight and in particular at least 99% by weight.
The average particle size of the second pesticide can be determined as D10,
D20 or 090
(i.e. particle size for which 10%, 20% or 90%, respectively, of the particles
are smaller).
Preferably, Dlo is smaller than 8.0 pm, particularly preferably smaller than
4.0 pm. In a
further preferred embodiment, D20 is smaller than 8.0 pm, particularly
preferably
smaller than 4.0 pm. In a further preferred embodiment, Dgo is smaller than
50.0 pm,
particularly preferably smaller than 25.0 pm. The average particle size is
usually
determined in accordance with CIPAC Method MT 187 "PARTICLE SIZE ANALYSIS
CA 02787550 2016-12-19
3
BY LASER DIFFRACTION".
Suitable alkyl lactates are Ci-C-12 alkyl lactates, where the alkyl radical
may be
branched or unbranched, saturated or unsaturated. The alkyl radical is
preferably
branched. The alkyl radical is preferably saturated. The alkyl radical is
particularly
preferably branched and saturated. Preferred alkyl lactates are C4-C8 alkyl
lactates,
particularly preferably C6-C8 alkyl lactates, in particular branched or
unbranched octyl
lactate. Examples of octyl lactates are 1-ethylhexyl, 2-ethylhexyl, 3-
ethylhexyl,
4-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl,
5-methylheptyl, 6-nnethylheptyl, or n-octyl. A preferred octyl lactate is 2-
ethylhexyl
lactate. The lactate group can be present in different stereoisomers, for
example as D-
or L-lactate. Preference is given to the L-lactate group. An especially
preferred alkyl
lactate is L-(2-ethylhexyl) lactate. The formulation can comprise one or more
alkyl
lactates, it preferably comprising exactly one alkyl lactate.
The formulation generally comprises 5 to 70% by weight of alkyl lactate,
preferably 10
to 60% by weight and in particular 15 to 50% by weight.
Suitable alcohols are all organic solvents with an alcohol group. Usually, the
melting
point of the alcohol is below 100 C, preferably below 40 C, and in particular
below
10 C. As functional groups, the alcohol comprises preferably only at least one
alcoholic
group, which may, for example, be a primary alcohol group or a phenolic
alcohol group.
The alcohol preferably comprises an aryl radical, which may comprise up to two
heteroatoms, such as phenyl radical or naphthyl radical. Particular preference
is given
to the alcohol benzyl alcohol or 2-(1-methylpropyl)phenol (also known as "o-
sec
butylphenol"), in particular benzyl alcohol. The formulation can comprise one
or more
alcohols, it preferably comprising exactly one alcohol.
The formulation comprises generally 1 to 50% by weight of alcohol, preferably
3 to 30%
by weight and in particular 7 to 18% by weight.
The weight ratio of alkyl lactate to alcohol is in most cases in the range
from 20/1 to
1/10, preferably from 8/1 to 1/3 and in particular from 5/1 to 1/1. Usually,
the alkyl
lactate and the alcohol form a homogeneous, continuous phase in the
formulation.
For example, the anhydrous formulation comprises:
a) a first pesticide in dissolved form,
b) a second pesticide in the form of suspended particles,
c) 5 to 70 (:)/0 by weight of a C4-C8 alkyl lactate, and
d) 3 to 30 `Yo by weight of an alcohol, wherein the alcohol comprises, as a
functional group, one alcoholic group; and wherein the weight ratio of alkyl
lactate
to alcohol is in the range from 8/1 to 1/3.
CA 02787550 2016-12-19
3a
The term pesticides refers to at least one active ingredient selected from the
group of
fungicides, insecticides, nematicides, herbicides, safeners and/or growth
regulators.
Preferred pesticides are epoxiconazole, pyraclostrobin, or metconazole..
Particularly
preferred pesticides are growth regulators. Mixtures of pesticides of two or
more of the
aforementioned classes can also be used. The person skilled in the art is
familiar with
such pesticides, which can be found, for example, in Pesticide Manual, 14th
Ed.
(2006), The British Crop Protection Council, London. Suitable pesticides are:
PF 70004 CA 02787550 2012-07-19
4
A) strobilurins:
azoxystrobin, dimoxystrobin, coumoxystrobin, coumethoxystrobin, enestroburin,
fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxystrobin,
methyl
242-(2,5-dimethylphenyloxymethyl)pheny1]-3-methoxyacrylate, 2-(2-(3-(2,6-di-
chloropheny1)-1-methylallylideneaminooxymethyl)pheny1)-2-methoxyimino-N-
methylacetamide;
B) carboxamides:
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid,
carboxin,
fenfuram, fenhexamid, flutolanil, fluxapyroxad, furametpyr, isopyrazam,
isotianil,
kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl,
oxycarboxin, penflufen penthiopyrad, sedaxane, tecloftalam, thifluzamide,
tiadinil, 2-
amino-4-methylthiazole-5-carboxanilide, N-(4'-trifluoromethylthiobipheny1-2-
y1)-3-
difluoromethy1-1-methy1-1H-pyrazole-4-carboxamide, N-(2-(1,3,3-trimethylbuty1)-
pheny1)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide;
- carboxylic acid morpholides: dimethomorph, flumorph, pyrimorph;
- benzamides: flumetover, fluopicolide, fluopyram, zoxamid;
- other carboxamides: carpropamid, diclocymet, mandipropamid,
oxytetracyclin,
silthiofam, N-(6-methoxypyridin-3-yl)cyclopropanecarboxamide;
C) azoles:
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole,
difenoconazole,
diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,
flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,
metconazole,
nnyclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole,
prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon,
triadimenol, triticonazole, uniconazole;
- imidazoles: cyazofamid, imazalil, imazalil sulfate, pefurazoate,
prochloraz,
triflumizole;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole, 2-(4-chloropheny1)-N14-(3,4-
dimethoxy-
phenyl)isoxazol-5-y1]-2-prop-2-ynyloxyacetamide;
D) nitrogenous heterocyclyl compounds
- pyridines: fluazinam, pyrifenox, 345-(4-chloropheny1)-2,3-
dimethylisoxazolidin-3-y1]-
pyridine, 345-(4-methylpheny1)-2,3-dimethylisoxazolidin-3-yllpyridine;
- pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone,
mepanipyrim,
nitrapyrin, nuarimol, pyrimethanil;
- piperazines: triforine;
- pyrroles: fludioxonil, fenpiclonil;
- morpholines: aldinnorph, dodemorph, dodemorph acetate, fenpropimorph,
tridennorph;
- piperidines: fenpropidin;
PF 70004 CA 02787550 2012-07-19
- dicarboximides: fluorimid, iprodione, procymidone, vinclozolin;
- nonaromatic 5-membered heterocyclic rings: famoxadon, fenamidon, flutianil,
octhilinone, probenazole, S-allyl 5-amino-2-isopropyl-3-oxo-4-orthotoly1-2,3-
dihydro-
pyrazole-1-thiocarboxylate;
5 - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S,
captafol, captan,
quinomethionate, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat
methylsulfate, fenoxanil, folpet, oxolinic acid, piperalin, proquinazid,
pyroquilon,
quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one,
5-chloro-1-(4,6-dimethoxypyrimidin-2-yI)-2-methyl-1H-benzimidazole, 5-chloro-7-
(4-
methylpiperidin-1-y1)-6-(2,4,6-trifluoropheny1)41,2,41triazolo[1,5-
a]pyrimidine, 5-ethyl-
6-octy141,2,4]triazolo[1,5-a]pyrimidin-7-ylamine;
E) carbamates and dithiocarbamates
- thio- and dithiocarbannates: ferbam, mancozeb, maneb, metam,
methasulphocarb,
metiram, propineb, thiram, zineb, ziram;
- carbamates: diethofencarb, benthiavalicarb, iprovalicarb, propamocarb,
propamocarb
hydrochloride, valiphenal, (4-fluorophenyl) N-(1-(1-(4-
cyanophenyl)ethanesulfonyI)-
but-2-yl)carbamate;
F) other fungicides
- guanidines: dodine, dodine free base, guazatine, guazatine acetate,
iminoctadine,
iminoctadine triacetate, iminoctadine tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxins,
streptomycin, validamycin A;
- nitrophenyl derivatives: binapacryl, dicloran, dinobuton, dinocap,
nitrothal-isopropyl,
tecnazene;
- organometallic compounds: fentin salts such as, for example, fentin acetate,
fentin
chloride, fentin hydroxide;
- sulfurous heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum,
iprobenfos,
phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: chlorthalonil, dichlofluanid, dichlorphen,
flusulfamide,
hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phthalide,
quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitrophenyI)-N-
ethyl-4-
methylbenzenesulfonannide;
- inorganic active substances: phosphorous acid and its salts, Bordeaux
mixture,
copper salts such as, for example, copper acetate, copper hydroxide, copper
oxychloride, basic copper sulfate, sulfur;
- biological products for controlling fungi, plant strengthening products:
Bacillus subtilis
strain NRRL No. B-21661 (for example the products RHAPSODY , SERENADE
MAX and SERENADE ASO from AgraQuest, Inc., USA.), Bacillus pumllus strain
NRRL No. B-30087 (for example SONATA and BALLAD Plus from AgraQuest,
Inc., USA), Ulocladium oudemansii(for example BOTRY-ZEN from BotriZen Ltd.,
New Zealand), chitosan (for example ARMOUR-ZEN from BotriZen Ltd., New
PF 70004 CA 02787550 2012-07-19
6
Zealand).
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine,
metrafenon,
mildiomycin, oxine-copper, prohexadione-calcium, spiroxamin, tolylfluanid, N-
(cyclo-
propylmethoxyimino-(6-difluoromethoxy-2,3-difluorophenypmethyl)-2-phenyl-
acetannide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylpheny1)-N-
ethyl-N-
methylformamidine, N'-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-
dimethylphenyI)-N-
ethyl-N-methylformamidine, N'-(2-methy1-5-trifluoromethy1-4-(3-
trimethylsilanyl-
propoxy)pheny1)-N-ethyl-N-methylformamidine, N'-(5-difluoromethy1-2-methy1-4-
(3-tri-
methylsilanylpropoxy)pheny1)-N-ethyl-N-methylformamidine, N-methyl-(1,2,3,4-
tetra-
hydronaphthalen-1-y1)-2-{142-(5-methy1-3-trifluoromethylpyrazol-1-
ypacetylipiperidin-
4-y1}thiazole-4-carboxylate,
N-methyl-(R)-1,2,3,4-tetrahydronaphthalen-1-y12-{142-(5-methy1-3-
trifluoromethylpyrazol-1-ypacetylipiperidin-4-yllthiazole-4-carboxylate, 6-
tert-buty1-8-
fluoro-2,3-dimethylquinolin-4-ylacetate, 6-tert-butyl-8-fluoro-2,3-
dimethylquinolin-4-y1
methoxyacetate, N-methy1-2-{112-(5-methy1-3-trifluoromethy1-1H-pyrazol-1-
ypacetyl]piperidin-4-yll-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-y1]-4-
thiazolecarboxamide;
G) growth regulators
abscisic acid, amidochlor, ancymidole, 6-benzylaminopurine, brassinolide,
butralin,
chlormequat (chlormequat chloride), choline chloride, cyclanilid, daminozide,
dikegulac,
dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol,
fluthiacet,
forchlorfenuron, gibberellic acid, inabenfid, indole-3-acetic acid, maleic
hydrazide,
mefluidid, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid,
N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium),
prohydrojasmone, thidiazuron, triapenthenol, tributylphosphorotrithioate,
2,3,5-triiodo-
benzoic acid, trinexapac-ethyl and uniconazole;
H) herbicides
- acetamide: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid,
flufenacet,
mefenacet, metolachlor, metazachlor, napropamid, naproanilid, pethoxamid,
pretilachlor, propachlor, thenylchlor;
- amino acid analogs: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop,
fluazifop,
haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- bipyridyls: diquat, paraquat;
- carbamates and thiocarbamates: asulam, butylate, carbetamide, desmedipham,
dimepiperat, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham,
prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim,
sethoxydim,
tepraloxydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin,
prodiamine,
trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen,
fomesafen,
CA 02787550 2012-07-19
PF 70004
7
lactofen, oyfluorfen;
- hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr;
- phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-0), 2,4-
DB,
dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone,
fluroxypyr,
picloram, picolinafen, thiazopyr;
- sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl,
chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron,
fluceto-
sulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron,
iodosulfuron,
mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron,
pro-
sulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron,
thifensulfuron, tria-
sulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-
chloro-6-propyl-
imidazo[1,2-b]pyridazin-3-yl)sulfony1)-3-(4,6-dimethoxypyrimidin-2-y1)urea;
- triazines: ametryne, atrazine, cyanazine, dimethametryne, ethiozine,
hexazinone,
metamitron, metribuzine, prometryne, simazine, terbuthylazine, terbutryne,
triaziflam;
- ureas: chlortoluron, daimuron, diuron, fluometuron, isoproturon, linuron,
methabenz-
thiazuron, tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-
methyl,
diclosulann, florasulam, flucarbazone, flumetsulam, metosulam,
orthosulfamuron,
penoxsu lam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalide,
pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin,
bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bromacil,
bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-
ethlyl,
chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamid, dicamba,
difenzoquat,
diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid,
fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, fluorochloridon,
flurtamon,
indanofan, isoxaben, isoxaflutol, lenacil, propanil, propyzamide, quinclorac,
quinmerac, mesotrione, methylarsenic acid, naptalam, oxadiargyl, oxadiazone,
oxaziclomefon, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl,
pyrasulfotol,
pyrazoxyfen, pyrazolynate, quinoclamin, saflufenacil, sulcotrione,
sulfentrazone,
terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-
312-(2-
methoxyethoxymethyl)-6-trifluoromethylpyridin-3-carbonyl]bicyclo[3.2.1]oct-3-
en-2-
one,
ethyl (342-chloro-4-fluoro-5-(3-methy1-2,6-dioxo-4-trifluoromethy1-3,6-dihydro-
2H-
pyrimidin-1-y1)phenoxy]pyridin-2-yloxy)acetate, methyl 6-amino-5-chloro-2-
cyclo-
propylpyrimidine-4-carboxylate, 6-chloro-3-(2-cyclopropy1-6-methylphenoxy)-
pyridazin-4-ol, 4-amino-3-chloro-6-(4-chlorophenyI)-5-fluoropyridin-2-
carboxylic acid,
methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridin-2-
carboxylate
PF 70004 CA 02787550 2012-07-19
8
and methyl 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluorophenyOpyridin-
2-
carboxylate;
I) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,
chlorpyrifos,
chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos,
dimethoat,
disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion,
methamidophos,
methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl,
paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate,
phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos,
tetrachlorvinphos,
terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl,
carbofuran,
carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl,
pirimicarb,
propoxur, thiodicarb, triazamate;
- pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,
cyphenothrin, cypermethrin,
alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin,
esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-
cyhalo-
thrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen,
tau-
fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin,
profluthrin,
dimefluthrin,
- insect growth inhibitors: a) chitin synthesis inhibitors: benzoylureas:
chlorfluazuron,
cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron,
lufenuron,
novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox,
etoxazole, clofentazin; b) ecdysone antagonists: halofenozide,
methoxyfenozide,
tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene,
fenoxycarb;
d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate;
- nicotine receptor agonists/antagonists: clothianidin, dinotefuran,
imidacloprid,
thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chlorothiazol-5-
ylmethyl)-
2-nitrimino-3,5-dimethy141,3,51triazinane;
- GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole,
pyrafluprole, pyriprole,
N-5-am ino-1-(2,6-dichloro-4-methylpheny1)-4-sulfinamoy1-1H-pyrazole-3-
thiocarbox-
amide;
- macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin,
spinosad,
spinetoram;
- mitochondrial electron transport chain inhibitor (METI) I acaricides:
fenazaquin,
pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI II and III substances: acequinocyl, fluacyprim, hydramethylnone;
- decouplers: chlorfenapyr;
- inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron,
fenbutatin oxide,
propargite;
- insect ecdysis inhibitors: cryomazin;
- 'mixed function oxidase' inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizon;
CA 02787550 2012-07-19
PF 70004
9
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozin,
sulfur,
thiocyclam, flubendiamid, chlorantraniliprole, cyazypyr (HGW86); cyenopyrafen,
flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and
pyrifluquinazone.
The first pesticide is preferably a pesticide which is soluble to at least 95%
by weight in
a mixture of 2-ethylhexyl lactate and benzyl alcohol (weight ratio 3:1) at 20
C. The first
pesticide is particularly preferably epoxiconazole, pyraclostrobin, or
metconazole,
specifically epoxiconazole or pyraclostrobin.
Besides the first pesticide, further pesticides may also be present in
dissolved form.
Preferred further pesticides which are present in dissolved form are
epoxiconazole or
pyraclostrobin.
The formulation comprises generally 0.01 to 50% by weight of the first
pesticide,
preferably 0.5 to 25% by weight and in particular 3 to 15% by weight.
The second pesticide is preferably a pesticide which is soluble to at most 5%
by weight
in a mixture of 2-ethylhexyl lactate and benzyl alcohol (weight ratio 3:1) at
20 C. The
second pesticide is particularly preferably boscalid, chlorothalonil, or
fluxapyroxad,
especially boscalid.
Besides the second pesticide, further pesticides may also be present in the
form of
suspended particles.
The formulation comprises generally 0.01 to 50% by weight of the second
pesticide,
preferably 1 to 30% by weight and in particular 8 to 20% by weight.
The weight ratio of the first to second pesticide is in most cases in the
range from 50/1
to 1/50, preferably from 5/1 to 1/10 and in particular from 2/1 to 1/4.
Furthermore, the formulations according to the invention may also comprise
customary
auxiliaries for agrochemical formulations, the choice of auxiliaries depending
on the
specific application form and/or the active ingredient. Examples of suitable
auxiliaries
are further solvents, solid carriers, surface-active substances (such as
surfactants,
solubilizers, protective colloids, wetting agent and tackifiers), organic and
inorganic
thickeners, bactericides, antifreezes, antifoams, optionally dyes and
adhesives (e.g. for
the treatment of seed material) or customary auxiliaries for bait formulation
(e.g.
attractants, feedants, bittering substances).
Besides the alcohol and the alkyl lactate, suitable further solvents are
organic solvents
such as mineral oil fractions of medium to high boiling point, such as
kerosene and
PF 70004 CA 02787550 2012-07-19
diesel oil, and also coal tar oils, and oils of vegetable or animal origin,
aliphatic, cyclic
and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylated
naphthalenes and derivatives thereof, alkylated benzenes and derivatives
thereof,
alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol,
glycols,
5 ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid
amides,
fatty acids and fatty acid esters and strongly polar solvents, e.g. amines
such as
N-methylpyrrolidone. In principle, it is also possible to use solvent
mixtures, and also
mixtures of the aforementioned solvents and water. Preferably, besides the
alcohol and
the alkyl lactate, the formulation comprises at most 20% by weight, preferably
at most
10 5% by weight and in particular at most 1% by weight, of further
solvents.
Solid carriers are mineral earths such as silicas, silica gels, silicates,
talc, kaolin,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate
and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as
ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable
products such as cereal meal, tree bark meal, wood meal and nutshell meal,
cellulose
powders or other solid carriers. The formulation preferably comprises no solid
carriers.
Suitable surface-active substances (adjuvants, wetting agents, tackifiers,
dispersants
or emulsifiers) are the alkali metal salts, alkaline earth metal salts,
ammonium salts of
aromatic sulfonic acids, e.g. of lignosulfonic acid (Borresperse grades,
Borregaard,
Norway), phenolsulfonic acid, naphthalenesulfonic acid (Morwet grades, Akzo
Nobel,
USA) and dibutylnaphthalenesulfonic acid (Nekal grades, BASF, Germany), and
also
of fatty acids, alkyl- and alkylarylsulfonates, alkyl ether, lauryl ether and
fatty alcohol
sulfates, and also salts of sulfated hexa-, hepta- and octadecanoles, and also
of fatty
alcohol glycol ethers, condensation products of sulfonated naphthalene and its
derivatives with formaldehyde, condensation products of naphthalene or of
naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene
octylphenol
ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol
ethers,
tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty
alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or
polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate,
sorbitol esters,
lignosulfite liquors, and also proteins, denatured proteins, polysaccharides
(e.g.
methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol
grades,
Clariant, Switzerland), polycarboxylates (Sokalan grades, BASF, Germany),
polyalkoxylates, polyvinylamine (Lupamin grades, BASF, Germany),
polyethylenimine
(Lupasol grades, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.
Suitable surfactants are in particular anionic, cationic, nonionic and
amphoteric
surfactants, block polymers and polyelectrolytes. Suitable anionic surfactants
are alkali
metal salts, alkaline earth metal salts or ammonium salts of sulfonates,
sulfates,
phosphates or carboxylates. Examples of sulfonates are alkylarylsulfonates,
PF 70004 CA 02787550 2012-07-19
11
diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of
fatty acids
and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed
naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of
naphthalenes
and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of
sulfates are
sulfates of fatty acid and oils, of ethoxylated alkylphenols, of alcohols, of
ethoxylated
alcohols, or of fatty acid esters. Examples of phosphates are phosphate
esters.
Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or
alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides,
amine
oxides, esters or sugar-based surfactants. Examples of alkoxylates are
compounds
such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or
fatty acid
esters which have been alkoxylated. For the alkoxylation, ethylene oxide
and/or
propylene oxide can be used, preferably ethylene oxide. Examples of N-
alkylated fatty
acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of
esters
are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-
based
surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters
or alkyl
polyglucosides.
Suitable cationic surfactants are quaternary surfactants, for example
quaternary
ammonium compounds with one or two hydrophobic groups, or salts of long-chain
primary amines. The formulation according to the invention comprises
preferably up to
5.0% by weight of cationic surfactants, particularly preferably up to 0.5% by
weight, and
specifically up to 0.05% by weight.
Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable
block
polymers are block polymers of the A-B or A-B-A type comprising blocks of
polyethylene oxide and polypropylene oxide or of the A-B-C type comprising
alkanol,
polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are
polyacids or
polybases. Examples of polyacids are alkali metal salts of polyacrylic acid.
Examples of
polybases are polyvinylamines or polyethyleneamines.
The formulation according to the invention can comprise 0.1 to 40% by weight,
preferably 1 to 30% by weight and in particular 2 to 20% by weight, total
amount of
surface-active substances and surfactants, based on the total amount of the
formulation.
Suitable thickeners are compounds which impart a modified flow behavior to the
formulation, i.e. a high viscosity in the resting state and low viscosity in
the agitated
state. Examples are polysaccharides, proteins (such as casein or gelatin),
synthetic
polymers, or inorganic layered minerals. Such thickeners are commercially
available,
for example xanthan gum (Kelzan , CP Kelco, USA), Rhodopol 23 (Rhodia,
France)
PF 70004 CA 02787550 2012-07-19
12
or Veegum (R.T. Vanderbilt, USA) or Attaclay (Engelhard Corp., NJ, USA).
Preferred
thickeners are inorganic layered minerals and polysaccharides, in particular
inorganic
layered minerals.
The content of thickener in the formulation depends on the effectiveness of
the
thickener. The person skilled in the art will choose a content in order to
obtain the
desired viscosity of the formulation. The content will in most cases be 0.01
to 10% by
weight.
Bactericides may be added for stabilizing the composition. Examples of
bactericides
are those based on diclorophen and benzyl alcohol hemiformal, and also
isothiazolinone derivatives such as alkylisothiazolinones and
benzoisothiazolinones
(Acticide MBS from Thor Chemie). Examples of suitable antifreezes are
ethylene
glycol, propylene glycol, urea and glycerol. Examples of antifoams are
silicone
emulsions (such as e.g. Silikon SRE, Wacker, Germany or Rhodorsil , Rhodia,
France), long-chain alcohols, fatty acids, salts of fatty acids,
organofluorine compounds
and mixtures thereof.
The user customarily uses the formulation according to the invention for
application in a
premetering device, in a rucksack sprayer, in a spray tank or in a spraying
aircraft.
Here, the formulation is brought to the desired use concentration with water
and/or
buffer, optionally with the addition of further auxiliaries, and thus giving
the ready-to-
use spray mixture (so-called tank mix). Usually, 50 to 500 liters of the ready-
to-use
spray mixture are applied per hectare of utilizable agricultural area,
preferably 100 to
400 liters. The active ingredient concentrations in the ready-to-use
preparations may
be varied within relatively large ranges. In general, they are between 0.0001
and 10%,
preferably between 0.01 and 1%.
Oils of various types, wetting agents, adjuvants, herbicides, bactericides,
other
fungicides and/or pesticides can be added to the active ingredients or to the
compositions comprising these, and optionally to the tank mix, immediately
prior to use.
These agents can be admixed to the compositions according to the invention in
the
weight ratio 1:100 to 100:1, preferably 1:10 to 10:1. Suitable adjuvants
within this
context are in particular: organically modified polysiloxanes, e.g. Break Thru
S 240 ;
alcohol alkoxylates, e.g. Atplus 245, Atplus MBA 1303, Plurafac LF 300 and
Lutensol ON 30; EO-PO block polymers, e.g. Pluronic RPE 2035 and Genapol B;
alcohol ethoxylates, e.g. Lutensol XP 80; and sodium dioctyl sulfosuccinate,
e.g.
Leophen RA.
Depending on the nature of the desired effect, the application rates when used
in crop
protection are between 0.001 and 2.0 kg of active ingredient per ha,
preferably
between 0.005 and 2 kg per ha, particularly preferably between 0.05 and 0.9 kg
per ha,
CA 02787550 2012-07-19
PF 70004
13
in particular between 0.1 and 0.75 kg per ha.
The present invention further relates to a method of controlling
phytopathogenic fungi
and/or undesired plant growth and/or undesired insect or mite infestation
and/or of
regulating the growth of plants, where the formulation according to the
invention is
allowed to act on the pests in question, their habitat or the plants to be
protected from
the particular pest, the soil and/or on undesired plants and/or the useful
plants and/or
their habitat.
The present invention further relates to the use of the formulation according
to the
invention for increasing the rain resistance of the applied pesticides.
The present invention further relates to the use of the formulation according
to the
invention for increasing the absorption of the applied pesticides into the
plant.
Advantages of the invention are that suspended active ingredients and
dissolved active
ingredients can now be combined in one formulation meaning that, for example,
it is
possible to dispense with laborious tank mixing of the individual formulation.
The
formulation is storage-stable (even upon repeated cooling below 0 C) and does
not
crystallize out. The pesticides have a high rain resistance. The pesticides
are absorbed
very rapidly and in large amounts into the leaf of the treated plant. The
pesticides
exhibit higher effectiveness compared to conventionally formulated active
ingredients.
The yield of the treated plants increases.
The examples below illustrate the invention without limiting it.
Examples
Nonionic surfactant A: alkoxylated fatty alcohol, liquid at 25 C; surface
tension for 1 g/I
in water at 23 C (DIN 53 914) 28 to 31 mN/m; cloud point according to EN 1890
Method A 21-22 C; setting point according to DIN 51583 ¨10 C
Nonionic surfactant B: polyaromatic ethoxylate, setting point 14 C; surface
tension for
0.1% in water at 25 C (DIN 53 914) 40 to 41 mN/m.
Nonionic surfactant C: organomodified siloxane, liquid, pH neutral in water,
setting
point -10 C.
Nonionic surfactant D: ethoxylate propoxylate of a short-chain fatty alcohol,
melting
point 30 C, surface tension for 0.1% in water at 25 C (DIN 53 914) 31-32 mN/m
Nonionic surfactant E: tristyrylphenol ethoxylate.
Nonionic surfactant F: castor oil, ethoxylated; liquid, water solubility 200
g/I; surface
tension 44-45 mN/m (OECD ring method).
Anionic surfactant A: polyetherphosphate, pH in water (100 g/I) at 23 C 2Ø
PF 70004
= CA 02787550 2012-07-19
14
Anionic surfactant B: alkylbenzenesulfonate 60% by weight dissolved in
branched
alcohol, setting point -31 C.
Thickener A: organically modified hectorite, finely divided powder.
Thickener B: sheet silicate based on an organically modified smectite, finely
divided
powder.
Example 1 - Epoxiconazole & boscalid in EHL & benzyl alcohol
Epoxiconazole was stirred in a mixture of 200 g of 2-ethylhexyl (S)-lactate
(EHL) and
125 g of benzyl alcohol until the active ingredient had dissolved. Then, the
other
formulation auxiliaries were added (see Table 1) and the mixture was stirred
for 10 min.
Finally, boscalid was added, and the mixture was stirred for 5 min and topped
up to
1.0 I with 2-ethylhexyl lactate. The resulting suspension was ground using a
ball mill.
The particle size was below 4 pm (50%) or below 25 pm (90%).
Stability test: the formulation was subjected to a temperature cycle from -10
C to
+10 C for one week. The formulation was stable and no deposition of the
suspended
particles was found. The viscosity of the formulation was likewise uniformly
stable. No
crystal growth was found either.
Example 2 - Epoxiconazole & pyraclostrobin & boscalid in EHL & benzyl alcohol
Epoxiconazole and pyraclostrobin were stirred in a mixture of 200 g of 2-
ethylhexyl
lactate and 125 g of benzyl alcohol until the two active ingredients had
dissolved. The
other formulation auxiliaries were then added (see Table 1) and the mixture
was stirred
for 10 min. Finally, boscalid was added, and the mixture was stirred for 5 min
and
topped up to 1.0 I with 2-ethylhexyl lactate. The resulting suspension was
ground using
a ball mill. The particle size was below 4 pm (50%) or below 25 pm (90%).
The stability test (see Example 1) again exhibited a stable formulation: the
formulation
was stable and no deposition of the suspended particles was found. The
viscosity of
the formulation was likewise uniformly stable. No crystal growth was found
either.
Example 3 - Epoxiconazole & boscalid in benzyl alcohol (not according to the
invention)
Epoxiconazole was stirred in a mixture of 300 g of benzyl alcohol until the
active
ingredient had dissolved. The other formulation auxiliaries were then added
(see
Table 1) and the mixture was stirred for 10 min. Finally, boscalid was added,
and the
mixture was stirred for 5 min and topped up to 1.0 I with benzyl alcohol. The
resulting
suspension was ground using a ball mill. The particle size was below 4 pm
(50%) or
below 25 pm (90%).
In the stability test (see Example 1), large crystals of boscalid were formed
and
irreversible phase separation was observed.
CA 02787550 2012-07-19
PF 70004
Example 4 - Epoxiconazole & boscalid in EHL (not according to the invention)
Epoxiconazole was stirred in a mixture of 300 g of 2-ethylhexyl lactate, the
active
ingredient becoming suspended. The other formulation auxiliaries were then
added
5 (see Table 1) and the mixture was stirred for 10 min. Finally, boscalid
was added, and
the mixture was stirred for 5 min and topped up to 1.0 I with 2-ethylhexyl
lactate. The
resulting suspension was ground using a ball mill. The particle size was below
4 pm
(50%) or below 25 pm (90%).
10 In the stability test (see Example 1), epoxiconazole was only partially
soluble.
Irreversible phase separation was observed.
Example 5 - Epoxiconazole & boscalid in EHL & benzyl alcohol & water (not
according
to the invention)
15 Epoxiconazole was stirred in a mixture of 200 g of 2-ethylhexyl lactate
and 125 g of
benzyl alcohol until the active ingredient had dissolved. The further
formulation
auxiliaries were then added (see Table 1), and the mixture was stirred for 10
min and
then topped up to 1.0 I with 2-ethylhexyl lactate (mixture A).
An aqueous suspension concentrate (280 ml) comprising 500 g/I of boscalid and
1.7%
by weight of phenolsulfonic acid-formaldehyde polycondensate sodium salt was
topped
up to 1.5 I with water. With slow stirring, mixture A was added and, finally,
the mixture
was topped up to 3.0 I with water. This gave an aqueous suspoemulsion.
In the stability test (see Example 1), crystals of epoxiconazole were formed.
The
suspoemulsion was not stable.
Table 1: Composition of Examples 1 to 5 (all concentrations in g/1)
Example No. 1 2 3a) 4a) 5a) 6a)
Boscalid 140 140 140 140 140 -
Epoxiconazole 50 50 50 50 50
Pyraclostrobin - 60 - - - 60
Nonionic surfactant A 100 100 100 100 100 100
Nonionic surfactant B 18 18 18 18 18 18
Thickener A 8 - 8 8 - -
Thickener B - 15 - - - 15
Anionic surfactant A 40 40 40 40 40 40
Nonionic surfactant C - 100 - - - 100
Nonionic surfactant D 18 18 18 18 18 18
Propylene carbonate 2.4 - 2.4 2.4 - , -
Nonionic surfactant E 60 60 60 60 60 60
Nonionic surfactant F - 50 - - - 50
Anionic surfactant B 24 24 24 24 24 24
PF 70004 CA 02787550 2012-07-19
16
Benzyl alcohol 125 125 ad 1 I 125 125
2-Ethylhexyl (S)-lactate ad 1 I ad 1 I ad 1 I ad 1 I ad 1 I
Water ad 3 I
a) not according to the invention
Example 6 - Rain resistance
Wheat plants (15 plants per pot, in each case 4 pots) were sprayed with the
formulations from Example 1 or 2, in each case with an application rate of 2.5
I/ha. For
comparison, one experimental series was not sprayed. One hour after spraying,
rain
was simulated in an amount of 30 mm. For comparison, in each case one
experimental
series was not subjected to rain. After 36 days, infestation with Septoria was
graded.
The results are summarized in Table 2. As comparison (not according to the
invention),
Bell from BASF SE was used (an aqueous suspension concentrate of 233 g/I
(20.8%
by weight) of boscalid and 67 g/I (6% by weight) of epoxiconazole, 11.2-12.6%
by
weight fatty alcohol alkoxylate), using the same application rate. The
experiment
showed that the rain resistance of the formulations according to the invention
is very
good.
Table 2: Rain resistance (% infestation with Septoria)
Formulation Without rain With rain With rain
[/o infestation] [/o infestation] [/0 infestation]
Without treatment 78 85 75
Example 1 0 0 0
Example 2 0 0 0
Bell a) 0 7 6
a) not according to the invention
Example 7 ¨ Spreading the spray drop on the leaf surface
To determine the spreading behavior of spray drops, spray mixtures were
prepared in
the customary field concentration in CIPAC water D. In each case, 1 pl drops
were
placed onto the leaf surface using a Hamilton syringe and the spreading of the
spray
drop during drying was visually monitored with the help of a stereomicroscope.
The
size of the drop immediately after placement (Fo) and the size of the drop
after drying
(FE) were measured. The experiments were repeated several times and the
averages
were calculated. Evaluation was carried out in accordance with the following
formula:
spreading factor (in percent) = FE:Fo x 100%.
The experiment showed the higher spreading formulation on leaf surfaces.
Table 3: Spreading
Spray mixture comprising formulation of Spreading factor
Example 1 > 1000%
Example 2 > 1000%
PF 70004 CA 02787550 2012-07-19
17
Bell a) ¨600%
a) not according to the invention
Example 8 - Active ingredient absorption
To determine the active ingredient absorption, wheat plants (melon, winter
wheat) were
grown in a greenhouse to stage 36 BBCH. The corresponding formulations (see
Table 4, 5) were applied in a laboratory spray track with the following
parameters:
product application rate: corresponding to the field concentration
water application rate: 200 I/ha
nozzle type: Lechler ID 120 02 (air injector flat-spray nozzle)
pressure: 3.33 bar
traveling speed: 5 km/h
Following application, the wheat plants were further cultivated again for 7
days in the
greenhouse. The treated leaves were then cut off and weighed. In a first step,
30-40 g
of leaves were cut up small into pieces measuring ca. 5 cm and washed with 200
ml of
methanol (50%). A further washing step then took place with 100 ml of methanol
(50%). The washing media were separated from the leaves, combined, and
analyzed
by means of LC-MS-MS (Table 4, 5 "Washable").
The leaves were then treated with 400 ml of extraction medium (70% methanol,
25%
water, 5% 2N HCI) and comminuted using a dispersing rod. One aliquot (ca. 10
ml) of
the supernatant was transferred to a centrifuge tube and centrifuged for 5 min
at
3000 rpm. 2 ml of the supernatant were placed in a test tube which comprised 2
ml of
0.2N NaOH. 5 ml of cyclohexane were added and the mixture is shaken for 20
min.
1 ml aliquot of the cyclohexane phase was pipetted into a chromatography vial
and
evaporated to dryness by means of nitrogen. The residue was taken up in 1 ml
of
methanol (50%), diluted and analyzed like the washing solution by means of LC-
MS-
MS (Table 4, 5 "Absorption").
The recovery rate of the various active ingredients was determined with
untreated
plants and active ingredient additions of 1 and 5 mg/kg of leaf mass. For
comparison,
the commercially available formulations Bell and Diamant0 (suspoemulsion, 114
g/I
of pyraclostrobin, 43 g/I of epoxiconazole, 214 g/I fenpropimorph, 17% by
weight of
solvent naphtha, 11% by weight of fatty alcohol alkoxylate, 5% by weight of
phenolsulfonic acid-formaldehyde polycondensate sodium salt) from BASF SE were
used, and also an aqueous suspension concentrate containing 160 g/I of
epoxiconazole, 260 g/I of pyraclostrobin ("Comparison A").
The experiments showed that the active ingredients formulated according to the
invention are better absorbed into the plants than known formulations of these
active
ingredients.
PF 70004 CA 02787550 2012-07-19
18
Table 4: Active ingredient absorption
Be110a) Example 1
Washable Absorption Washable Absorption
Epoxiconazole 75 25 29 71
Boscalid 94 6 92 8
a) not according to the invention
Table 5: Active ingredient absorption
Comparison A a) Belle+ Diamant a), b)
Example 2
Washable Absorption Washable Absorption Washable Absorption
Epoxiconazole 90 10 63 37 21 79
Boscalid 91 9 90 10
Pyraclostrobin 92 8 66 34 52 48
a) not according to the invention; b) weight ratio 1/1.
Example 9 - Biological effectiveness
The biological effectiveness against Septoria triticiwas tested on wheat
plants in field
experiments upon use to BBCH 31-59. 21-42 days after application, the
infestation of
Septoria was graded and the efficacy was calculated. Whereas in the case of
plants
treated with Bell , an average efficacy (n = 4) of 72% was found, the
formulation from
Example 1 exhibited an average effectiveness of 90%.
Example 10- Yield increase
The yield of wheat was measured in field experiments in Europe. The untreated
fields
had on average (n = 13) a yield of 85.1 dt/ha, the fields treated with Bell
97.8 dt/ha
and the fields treated with the formulation from Example 1101.6 dt/ha.
Example 11 - Biological effectiveness
The biological effectiveness against net blotch was tested on barley plants
upon use to
BBCH 31-62. 21-42 days after application, the infestation was graded and the
efficacy
calculated. Whereas in the case of the plants treated with Bell an average
effectiveness (n = 8) of 71% was found, the formulation from Example 1
exhibited an
average effectiveness of 84%.
Example 12 - Biological effectiveness
The biological effectiveness against brown rust was tested on winter wheat
upon use to
BBCH 32-59. 30-50 days after application, the infestation was graded and the
efficacy
calculated. Whereas in the case of the plants treated with Bell an average
effectiveness (n = 6) of 83% was found, the formulation from Example 1
exhibited an
average effectiveness of 88%, and the formulation from Example 2 an average
effectiveness of 95%.
PF 70004 CA 02787550 2012-07-19
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Example 13 - Biological effectiveness
The biological effectiveness against Rhynchosporium was tested on barley upon
use to
BBCH 31-49. 20-50 days after application, the infestation was graded and the
efficacy
calculated. Whereas in the case of the plants treated with Bell an average
effectiveness (n = 4) of 55% was found, the formulation from Example 1
exhibited an
average effectiveness of 65%, and the formulation from Example 2 an average
effectiveness of 77%.
