Note: Descriptions are shown in the official language in which they were submitted.
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AOUEOUS NEONICOTINOID COMPOSITIONS FOR SEED TREATMENT
Technical Field
The present invention relates to aqueous compositions, to the preparation of
such
compositions and to a method of using such compositions for controlling
insects and/or
representatives of the order Acarina. The aqueous compositions of the
invention have
particular application in the protection of plant propagation materials, such
as seeds,
against insects and/or representatives of the order Acarina.
Background
The use of synthetic insecticides to control insect pests in crops is a
universal practice.
This practice has gained a high degree of commercial success because it has
been
shown that such control can increase crop yield. However, effective use of
insecticides
requires sound management in view of insect resistance and environmental and
worker
exposure concerns. One solution applied to this problem has been the provision
of new,
more highly active insecticides in order to reduce the need for older acutely
toxic
insecticides and to reduce environmental loading rates.
One new class of insecticides that is gaining significant recognition in the
market place is
the so-called "neonicotinoid" insecticides. Insecticides of this class include
nitroimino- or
nitroguanidino-compounds, for example, the compounds imidacloprid,
acetamiprid, and
thiamethoxam that are described in U.S. patent nos. 4742060 and 5304566 and
EP580553A2, respectively.
Direct treatment of plant propagation materials (such as seeds) with
insecticides are
target applications which address the need for a reduction of environmental
and worker
exposure and pest resistance buildup when applied alone or in conjunction with
foliar or
furrow insecticide applications.
Seed treatments are used on a large variety of crops to control a large
variety of pests.
Seed treatments are commonly used to ensure uniform stand establishment and
reducing yield loss by protecting the seedling against soil-borne insects.
Systemic seed
treatments may provide an alternative to traditional broadcast sprays of
foliar
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insecticides in some instances.
Insecticide seed treatments come in a variety of formulations: dry flowables
(DF), liquid
flowables (LF), true liquids (TL), emulsifiable concentrates (EC), dusts (D),
wettable
powders (WP), suspoemulsions (SE), water-dispersible granules (WG) and others.
Some are registered for use only by commercial applicators using closed
application
systems, others are readily available for on-farm use as dusts, slurries,
water-soluble
bags, or liquid ready-to-apply formulations.
i0 Commercial seed treatment is often desirable due to the specialized
equipment required
to properly apply treatments or to treat large volumes of seed. An important
concern of
the commercial treater is equipment performance to ensure the delivery of a
proper
amount of active ingredient to the seed. This has become especially important
with
more modern insecticides that require only very small amounts of material
(down to 1 g
active ingredient per hundred weight of seed).
Conveniently, many seed treatment materials also are available for on-farm
use. These
are known as hopper-box or planter-box treatments wherein liquid or dry
formulations
are applied to seed as it passes through an auger from the transport bin or
truck to the
planter boxes. These formulations are a very convenient way to apply seed
treatment
onto bulk seed right before planting. Conventional dry treatments generally
are
formulated with talc or graphite which adheres the treatment chemical to the
seed.
Conventional liquid hopper-box treatments generally are made available as a
fast-drying
formulations. In any case, good seed coverage is required for maximum benefit
from
any seed treatment formulation.
However, obtaining thorough seed coverage can be difficult when attempting to
treat
seed. For example, dry formulations can present unacceptable worker exposure
to the
insecticidal active ingredient. Certain liquid formulations can become
inhomogeneous
on storage, such that particle size or viscosity do not remain constant.
Additional
problems can arise such as unacceptable drying times, material build-up in the
seed
treater, low seed flowability, poor seed coverage and dust-off of the
insecticide from the
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seed prior to planting. As a result, handling is rendered difficult and the
biological
efficacy of the seed treatment is reduced.
There is a need in the art for alternative new liquid insecticidal seed
treatment
compositions that are effective for use with both commercial and on-farm seed
treatment
equipment.
Summary
It has now been found, surprisingly, that specific filled aqueous insecticidal
compositions
based on the combination of a surfactant, an inorganic carrier, an antifreeze
agent and
an insecticide of the neonicotinoid class are storage stable, have improved
flowability
and have good adherence to plant propagation material with low dust-off, and
have
excellent performance on cold or frozen seed. The aqueous compositions of the
invention have particular application in the protection of plant propagation
materials,
such as seeds, against insects and/or representatives of the order Acarina,
but also are
advantageously combined with fungicidally active compounds to control
phytopathogenic
fungi.
The present invention thus provides an aqueous composition suitable for
applying
insecticides or acaricides to plant propagation materials comprising water, an
insecticidally or acaricidally effective amount of at least one nitroimino- or
nitroguanidino-
compound in free form or in agrochemically useful salt form and a blend of the
following
components, by weight:
a) 2- 10% of a surface-active agent comprising al) at least one anionic
surfactant;
b) 4- 20% of at least one inorganic solid carrier; and
c) 3- 25% of at least one antifreeze agent.
In one embodiment, the aqueous composition further comprises a fungicidally
effective
amount of at least one fungicidally active compound.
The aqueous compositions are prepared by intimately mixing the components with
water, optionally using a concentrated premix prepared by wet milling the
solid
components, until an evenly dispersed phase is achieved.
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The invention also provides for plant propagation materials
treated with the aqueous composition and for a method for
reducing insect or acarinal infestation of plant propagation
materials such as seeds and seedlings. The method comprises
contacting the seeds with an aqueous insecticidal/acaricidal
composition according to the invention described above.
According to one aspect of the present invention, there is
provided a formulated insecticidal aqueous composition for
applying to plant propagation material comprising water,
between about 25% to about 35% of at least one compound
selected from the group consisting of thiamethoxam,
imidacloprid, thiacloprid, nitenpyram and acetamiprid,
and a blend of the following components, by weight:
a) 2 - 100 of at least one surface-active agent, comprising
al) at least one anionic surfactant;
b) 4 - 20% of at least one inorganic solid carrier; and
c) 3 - 20% of at least one antifreeze agent.
According to another aspect of the present invention, there
is provided a formulated insecticidal aqueous composition
for applying to plant propagation material comprising water,
between about 20% to about 35% of clothianidin
and a blend of the following components, by weight:
a) 2 - 10% of at least one surface-active agent, comprising
al) at least one anionic surfactant;
b) 4 - 20% of at least one inorganic solid carrier; and
c) 3 - 20% of at least one antifreeze agent.
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According to still another aspect of the present invention,
there is provided a use of a composition as described herein
for treating plant propagation material to render the plant
propagation material insect-resistant.
According to yet another aspect of the present invention,
there is provided a method of protecting plant propagation
material against attack by insects and phytopathogenic fungi
which comprises treating said plant propagation material
with an insecticidally effective amount of a composition as
described herein and a fungicide.
According to a further aspect of the present invention,
there is provided a storage and shipping system comprising a
container ranging in capacity from about 0.1 liter to about
10 liters substantially filled with a formulated aqueous
composition as described herein.
Detailed Description
The inventors have discovered that a specific combination of
surfactants (a), carriers (b) and antifreeze agents (c) and
a neonicotinoid insecticide when used together provide
aqueous compositions that are storage stable and are
suitable for use in normal seed treatment equipment, such as
a slurry seed treater, direct treater, panogen treater or a
mist-o-matic treater as well as on-farm hopper-box or
planter-box treatments. Propagation materials treated with
the aqueous compositions dry quickly, have good flowability,
suitable coverage and have little or no dust-off.
Active Ingredients
The term insecticide or insecticidally when used herein in
connection with neonicotinoid compounds is intended to
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include or refer to both insecticidally and acaricidally
active compounds.
The term nitroimino- or nitroguanidino-compound as utilized
herein is intended to cover insecticidally and/or
acaricidally active compounds of the so-called neonicotinoid
class. In one embodiment, suitable nitroimino- or
nitroguanidino-compounds include at least one neonicotinoid
compound of formula (I)
R1
AyY (I),
X
wherein
A is 2-chloropyrid-5-yl, 2-methylpyrid-5-yl,
1-oxido-3-pyridinio, 2-chloro-l-oxido-5-pyridinio,
2,3-dichloro-l-oxido-5-pyridinio, tetrahydrofuran-3-yl,
5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl group,
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Y is -N(R)(R2), SR2 or C,-C4-alkyl;
R is hydrogen, C,-C6alkyl, phenyl-C,-C4alkyl, C3-Cscycloalkyl, C2-Csalkenyl or
C2-Csalkynyl;
R, and R2 are independently of each other C,-Ca-alkyl, C,-C4-alkenyl, C,-C4-
alkinyl ,
-C(=O)-CH3 or benzyl; or together form a group -CH2-CH2-, -CHZ-CH2-CH2-,
-CH2-O-CH2-, -CH2-S-CH2-, -CH2-NH-CH2- or -CH2-N(CH3)-CH2-; and
X is N-NO2, N-CN or CH-NO2; or, where appropriate, a tautomer thereof, in each
case in
free from or in salt form.
lo The compounds (I) may be in the form of tautomers. Accordingly,
hereinbefore and
hereinafter, where appropriate the compound (I) are to be understood to
include
corresponding tautomers, even if the latter are not specifically mentioned in
each case.
The compounds of the formula (I) are capable of forming acid addition salts.
Those salts
are formed, for example, with strong inorganic acids, such as mineral acids,
for example
perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid
or a hydrohalic
acid, with strong organic carboxylic acids, such as unsubstituted or
substituted, for
example halo-substituted, C,-C4alkanecarboxylic acids, for example acetic
acid,
saturated or unsaturated dicarboxylic acids, for example oxalic, malonic,
succinic,
maleic, fumaric or phthalic acid, hydroxycarboxylic acids, for example
ascorbic, lactic,
malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic
acids, such as
unsubstituted or substituted, for example halo-substituted, C,-C4alkane- or
aryl-sulfonic
acids, for example methane- or p-toluene-sulfonic acid. Furthermore, compounds
of
formula (1) having at least one acidic group are capable of forming salts with
bases.
Suitable salts with bases are, for example, metal salts, such as alkali metal
or alkaline
earth metal salts, for example sodium, potassium or magnesium salts, or salts
with
ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a
mono-, di-
or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-
propyl-amine, or
a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-
ethanolamine.
In addition, corresponding internal salts may also be formed. As a particular
subset
within the scope of the invention there may be mentioned agrochemically
advantageous
salts. In view of the close relationship between the compounds of formula (t)
in free form
and in the form of their salts, any reference hereinbefore or hereinafter to
the free
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compounds of formula (I) or to their respective salts is to be understood as
including also
the corresponding salts or the free compounds of formula (I), where
appropriate and
expedient. The same applies in the case of tautomers of compounds of formula
(I) and
the salts thereof. In each case, the free form is particularly suitable.
Specific compounds of the formula (I) are those wherein
A is a pyrid-3-yl, 2-chloropyrid-5-yl, 2-chloro-1-oxido-5-pyridinio or 2-
chlorothiazol-5-yl
group; particularly a 2-chloropyrid-5-yi group or a 2-chlorothiazol-5-yl
group;
wherein Y is -N(R)(R2);
io R is C,-Csalkyl, phenyl-C,-C4alkyl, C3-C4alkenyl or C3-C4alkynyl;
more especially C,-Caalkyl, such as methyl;
R, and R2 are independently of each other C,-C4-alkyl or benzyl, or together a
group
-CHZ-CH2-, -CH2-CH2-CH2-, -CH2-O-CH2-, -CH2-S-CH2-, -CH2-NH-CH2-,
-CH2-N(CH3)-CH2-, especially -CH2-CH2- or -CH2-O-CH2-, particularly -CHZ-O-CH2-
; and
X is N-NO2 or N-CN, more especially N-NO2.
Specific examples of suitable neonicotinoids within the scope of the invention
include
CI)-1-S
thiamethoxam of the formula N~,N N,
CH Y 3
N
" NO2
CI /
imidacloprid of the formula N~ N N, H ~
II
NO2
CI y
thiacloprid of the formula NN S
Y p
N" CN
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Ci
s
H CH
Clothianidin of the formula N N N
, H
NO2
cl N
~ 8t
Nitenpyram of the formula I ; and
$ NO 2
NHHe
cl
acetamiprid of the formula ~~ 1'' ~~'
i 1 (I
ca $ - N- c- Ne
The neonicotinoid compounds are employed in an insecticidally or acaricidally
effective
amount in the composition.
Mixtures of one or more of the foregoing active compounds also are usable as
an active
component in the practice of the present invention.
In one embodiment, the insecticidally or acaracidally active compound or
compound
mixture is present in the composition in an amount of from about 0.5 % to
about 50% by
weight, more particularly from 2 to about 35% w/w, and more particularly from
about
20% to about 30% w/w.
In another embodiment, the insecticidally or acaracidally active compound or
compound
mixture includes neonicotinoid compounds selected from the group consisting of
thiamethoxam, imidacloprid, thiacloprid, nitenpyram and acetamiprid in amounts
2o between about 25% to about 35% or clothianidin in an amount between about
20% to
about 35%.
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The term "fungicide" as utilized herein is intended to cover compounds active
against
phytopathogenic fungi that may belong to a very wide range of compound
classes.
Examples of compound classes to which the suitable fungicidally active
compound may
belong include both room temperature (25 C) solid and room temperature liquid
fungicides such as: triazole derivatives, strobilurins, carbamates (including
thio- and
dithiocarbamates), benzimidazoles (thiabendazole), N-trihalomethylthio
compounds
(captan), substituted benzenes, carboxamides, phenylamides and phenylpyrroles,
and
mixtures thereof.
Examples of suitable individual compounds of the above mentioned compound
classes
are listed below. Where known, the common name is used to designate the
individual
compounds (q.v. the Pesticide Manual, 12th edition, 2001, British Crop
Protection
Council).
Suitable triazole derivatives include propiconazole, difenconazole,
tebuconazole,
tetraconazole and triticonazole.
Suitable strobilurins include trifloxystrobin, azoxystrobin, kresoxim-methyl
and
picoxystrobin.
Suitable carbamates include thiram.
Suitable substituted benzenes include PCNB and chlorothalonil.
Suitable carboxamides include carboxin.
Specific phenylamides usable in the compositions and methods falling within
the scope
of the present invention include metalaxyl; metalaxyl consisting of more than
70% by
weight of the R-enantiomer; metalaxyl consisting of more than 85% by weight of
the R-
enantiomer; metalaxyl consisting of more than 92% by weight of the R-
enantiomer;
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metalaxyl consisting of more than 97% by weight of the R-enantiomer; and
mefenoxam
(i.e., R-metalaxyl or metalaxyl-M).
A specific phenylpyrrole usable in the compositions and methods failing within
the scope
of the present invention is fludioxonil.
Other suitable fungicidal compounds that may mentioned are Benomyl (also known
as
TM
Benlate), Bitertanol, Carbendazim, Capropamid, Cymoxanil, Cyprodinil,
Ethirimol,
Fenpicionil, Fenpropimorph, Fluquinconazole, Flutolanil, Flutriafol, Fosetyl-
aluminum,
l0 Fuberidazole, Guazatine, Hymexanol, Kasugamycin, Imazalil, Imibenconazole,
Iminoctadine-triacetate, lpconazole, Iprodione, Mancozeb, Maneb, Mepronil,
Metalaxyl,
TM
Metalaxyl-M (Mefenoxam), Metconazole, Metiram, MON 65500 (Silthiopham-ISO
proposed), Myclobutanil, Nuarimot, Oxadixyl, Oxine-copper, Oxolinic acid,
Pefurazoate,
Pencycuron, Prochloraz, Propamocarb hydrochloride, Pyroquilon, Silthiopham -
see
is MON 65500, Tecnazene, Thifluzamide, Thiophenate-methyl, Tolclofos-methyl,
Triadimenol, Triazoxide and Triflumizole.
The fungicidally active compounds are employed in a fungicidally effective
amount in the
composition.
Mixtures of one or more of the foregoing fungicidally active compounds also
are usable
as an active component in the practice of the present invention.
In one embodiment, mixtures of at least one ambient liquid fungicide (for
example, a
phenylamide such as R-metataxyl) and at least one ambient solid fungicide (for
example,
a phenylpyrrole such as fludioxonil) are employed.
In one embodiment, the fungicidally active compound or compound mixture is
present in
the composition in an amount of from about 0.5 % to about 50 % by weight, more
specifically, from 2 to about 20% by weight of the entire composition.
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Surface Active Agent
The aqueous compositions contain at least about 2% up to about 10% by weight
of a
surface-active agent (a). In one embodiment, the aqueous compositions contain
from
3% up to 7% by weight of a surface-active agent (a).
The surface active agent (a) comprises (al) at least one anionic surfactant.
In general,
the anionic surfactant may be any known in the art. Suitable anionic
surfactants are in
general oligomers and polymers, as well as polycondensates, which contain a
sufficient
number of anionic groups to ensure their water-solubility. Suitable anionic
surfactants
lo include alcohol sulfates, alcohol ether sulfates, alkylaryl ether sulfates,
alkylaryl
sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates and
salts
thereof, alkyl sulfonates, mono- or di-phosphate esters of polyalkoxylated
alkyl alcohols
or alkylphenols , mono- or di-sulfosuccinate esters of C12-C,5 alkanols or
polyalkoxylated
C12-C,5 alkanols, alcohol ether carboxylates, phenolic ether carboxylates,
polybasic acid
esters of ethoxylated polyoxyalkylene glycols consisting of oxybutylene or the
residue of
tetrahydrofuran, sulfoalkylamides and salts thereof such as N-methyl--N-
oleoyltaurate
Na salt, polyoxyalkylene aikylphenol carboxylates, polyoxyalkylene alcohol
carboxylates
alkyl polyglycoside/alkenyl succinic anhydride condensation products, alkyl
ester
sulfates, napthalene sulfonates, naphthalene formaldehyde condensates, alkyl
sulfonamides, sulfonated aliphatic polyesters, sulfate esters of styrylphenyl
alkoxylates,
and sulfonate esters of styrylphenyl alkoxylates and their corresponding
sodium,
potassium, calcium, magnesium, zinc, ammonium, alkylammonium,
diethanolammonium, or triethanolammonium salts, salts of ligninsulfonic acid
such as
the sodium, potassium, magnesium, calcium or ammonium salt, polyaryiphenol
polyalkoxyether sulfates and potyarylphenol polyalkoxyether phosphates, and
sulfated
alkyl phenol ethoxylates and phosphated alkyl phenol ethoxylates.
TM
Specific examples of suitable anionic surfactants include: Geropon T77
(Rhodia) (N-
TM.
methyl--N-oleoyltaurate Na salt); Soprophor 4D384 (Rhodia) (tristyrylphenol
sulphate);
TM TM
3o Reax 825 (Westvaco) (ethoxylated lignin sulfonate); Stepfac 8171 (Stepan)
(ethoxylated
TM
nonylphenol phosphate ester); Ninate 401-A (Stepan) (calcium alkylbenzene
sulfonate);
TM TMI
Emphos CS-131 (Witco) (ethoxylated nonylphenol phosphate ester); Atphos 3226
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(Uniquema) (ethoxylated tridecylalcohol phosphate ester). Suitable anionic
surfactants
can be prepared by methods known per se and also are commercially available.
The surface-active agent comprising al) at least one anionic surfactant may
optionally
further comprise a2) one or more nonionic surfactants. As used herein,
"nonionic
surfactants" are different compounds from the water-dispersible and water-
soluble
polymers b) described herein.
Exemplary nonionic surfactants include polyarylphenol polyethoxy ethers,
lo polyalkylphenol polyethoxy ethers, polyglycol ether derivatives of
saturated fatty acids,
polyglycol ether derivatives of unsaturated fatty acids, polyglycol ether
derivatives of
aliphatic alcohols, polyglycol ether derivatives of cycloatiphatic alcohols,
fatty acid esters
of polyoxyethylene sorbitan, alkoxylated vegetable oils, alkoxylated
acetylenic diols,
polyalkoxylated alkylphenols, fatty acid alkoxylates, sorbitan aikoxylates,
sorbitol esters,
C8-C22 alkyl or alkenyl polyglycosides, polyalkoxy styrylaryl ethers,
atkylamine oxides,
block copotymer ethers, polyalkoxylated fatty glyceride, polyalkylene glycol
ethers, linear
aliphatic or aromatic polyesters, organo silicones, polyaryl phenols, sorbitol
ester
alkoxylates, and mono- and diesters of ethylene glycol and mixtures thereof.
TM
Specific examples of suitable nonionic sufactants include: Genapol X-060
(Clariant)
TM
(ethoxylated fatty alcohol); Sorpohor BSU (Rhodia) (ethoxylated
tristyrylphenol); MakonM
TM
TD-6 (Stepan) (ethoxylated fatty alcohol); BRIJ 30 (Uniquema) (ethoxylated
lauryl
TM TM
alcohol); Witconol CO-360 (Witco) (ethoxylated castor o'il); Witconol NP-60
(Witco)
(ethoxytated nonylphenol). Suitable nonionic surfactants can be prepared by
methods
known per se and also are commercially availabte.
In addition to anionic and nonionic surfactants, certain cationic or
zwitterionic surfactants
a3) also are suitable for use in the present invention such as alkanol amides
of CB-C,8
fatty acids and Ce-C18 fatty amine polyalkoxylates, C,o-C18
3o alkyidimethylbenzylammonium chlorides, coconut alkyldimethylaminoacetic
acids, and
phosphate esters of Ca-18 fatty amine polyalkoxylates.
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Carrier
The aqueous composition also comprises (b), at least about 4 and up to about
20%,
more specifically from 5 to about 15% of at least one inorganic solid carrier.
The inorganic solid carrier is a natural or synthetic solid material that is
insoluble in
water. This carrier is generally inert and acceptable in agriculture,
especially on the
treated seed or other propagation material. It can be chosen, for example,
from clay,
natural or synthetic silicates, titanium dioxide, magnesium silicate, aluminum
silicate,
talc, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk,
diatomaceous earth,
1o lime, calcium carbonate, bentonite clay, Fuller's earth, and the like such
as described in
the CFR 180.1001. (c) & (d).
Antifreeze
The aqueous composition also comprises (c), at least about 3 and up to about
25% of at
least one antifreeze agent, more specifically from 6 to about 20% by weight.
Specific examples of suitable antifreezes include ethylene glycol, 1,2-
propylene glycol,
1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-
pentanediol, 3-
methyl-1,5-pentanediol, 2,3-dimethyl-2,3-butanediol, trimethylol propane,
mannitol,
sorbitol, glycerol, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol,
bisphenois such
as bisphenol A or the like. In addition, ether alcohols such as diethylene
glycol,
triethylene glycol, tetraethylene glycol, polyoxyethylene or polyoxypropylene
glycols of
molecular weight up to about 4000, diethylene glycol monomethylether,
diethylene glycol
monoethylether, triethylene glycol monomethylether, butoxyethanol, butylene
glycol
monobutylether, dipentaerythritol, tripentaerythritol, tetrapentaerythritol,
diglycerol,
triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol,
octaglycerol and the
like.
3o As a particular subset of suitable antifreeze materials there can be
mentioned ethylene
glycol, propylene glycol and glycerin.
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Additional Components
The aqueous composition optionally includes (d) at least one polymer selected
from
water-soluble and water-dispersible film-forming polymers. Suitable polymers
have an
average molecular weight of at least about 1,000 up to about 100,000; more
specifically
at least about 5,000, up to about 100,000. The aqueous compositions generally
contain
from about 0% to about 10% by weight of the composition of polymer (d). In a
specific
embodiment, the compositions contain from about 1.0% upto about 5% by weight
of a
film-forming polymer (d).
1o Suitable polymers are selected from
dl) alkyleneoxide random and block copolymers such as ethylene oxide-propylene
oxide
block copolymers (EO/PO block copolymers) including both EO-PO-EO and PO-EO-PO
block copolymers;
ethylene oxide-butylene oxide random and block copolymers,
CZ.s alkyl adducts of ethylene oxide-propylene oxide random and block
copolymers,
C2.6 alkyl adducts of ethylene oxide-butylene oxide random and block
copolymers,
d2) polyoxyethylene-polyoxypropylene monoalkylethers such as methyl ether,
ethyl
ether, propyl ether, butyl ether or mixtures thereof.
d3) vinylacetate/vinylpyrrolidone copolymers,
d4) alkylated vinylpyrrolidone copolymers,
d5) polyvinylpyrrolidone, and
d6) polyalkyleneglycol including the polypropylene glycols and polyethylene
glycols.
TM
Specific examples of suitable polymers include Pluronic P103 (BASF) (EO-PO-EO
block
TM TM
copolymer), Pluronic P65 (BASF) (EO-PO-EO block copolymer), Pluronic P108
(BASF)
TM
(EO-PO-EO block copolymer), Vinamul 18160 (National Starch)
(polyvinylacetate),
TM TM
Agrimer 30 (ISP) (polyvinylpyrrolidone), Agrimer VA7w (ISP) (vinyl
TM'
acetate/vinylpyrrolidone copolymer), Agrimer AL 10 (ISP) (alkylated
vinylpyrrolidone
CA 02567615 2008-02-22
30989-29(S)
-14-
TM
copolymer), PEG 400 (Uniqema) (polyethylene glycol), Pluronic R 25R2 (BASF)
(PO-
TM
EO-PO block copolymer), Pluronic R 31 Ri (BASF) (PO-EO-PO block copolymer) and
TM
Witconol NS 500LQ (Witco) (butanol PO-EO copolymer).
The composition aiso optionally contains (e) at least one thickener.
In one embodiment, the thickener is present in the aqueous composition in an
amount
from about 0.01% to about 25% w/w, more specifically from 0.02 to 10% by
weight.
i o Illustrative of thickeners (water-soluble polymers which exhibit
pseudoplastic properties
in an aqueous medium) are gum arabic, gum karaya, gum tragacanth, guar gum,
locust
bean gum, xanthan gum, carrageenan, alginate salt, casein, dextran, pectin,
agar, 2-
hydroxyethyl starch, 2-aminoethyl starch, 2-hydroxyethyl cellulose, methyl
cellulose,
carboxymethyl cellulose salt, cellulose sulfate salt, polyacrylamide, alkali
metal salts of
the maleic anhydride copolymers, alkali metal salts of poly(meth)acrylate, and
the like.
As suitable thickeners there may also be mentioned attapulgite-type clay,
carrageenan,
croscarmellose sodium, furcelleran, glycerol, hydroxypropyl methylcellulose,
polystyrene, hydroxypropyl cellulose, hydroxypropyl guar gum, and sodium
carboxymethylcellulose. Xanthan gum is preferred.
The aqueous composition according to the invention can be employed together
with the
adjuvants customary in formulation technology, biocides, biostats, emulsifiers
(lethicin,
sorbitan, and the like), antifoam agents or application-promoting adjuvants
customarily
employed in the art of formulation. In addition, there may be mentioned
inoculants and
brighteners.
Additionally, a coloring agent, such as a dye or pigment is included in the
seed coating
so that an observer can immediately determine that the seeds are treated. The
dye is
also useful to indicate to the user the degree of uniformity of the coating
applied.
The inventive compositions contain and/or may be applied together or
sequentially with
further active compounds. These further compounds can be fertilizers or
micronutrient
CA 02567615 2008-02-22
30989-29(S)
-15-
donors or other preparations that influence plant growth. They can also be
selective
herbicides, fungicides, other insecticides, bactericides, insect growth
regulators, plant
growth regulators, nematicides, molluscicides or mixtures of several of these
preparations.
Process
The aqueous neonicotinoid compositions of the invention can be prepared by
processes
known in the art.
In one embodiment, the aqueous neonicotinoid compositions of the invention can
be
prepared by a process which comprises the steps: (a) forming a premix with at
least one
solid active compound and at least one surfactant; (b) forming a premix of a
carrier and
water, and (c) sequentially adding the premixes (a) and (b) and the remaining
ingredients to water while stirring to form as evenly dispersed composition.
In one aspect, the solid active compounds may be wet milied prior to being
added to the
mixture (c).
The final composition can be screened if desired to remove any insoluble
particles.
Aqueous Composition
Insecticidal compositions in accordance with the invention may take the form
of aqueous
solutions, dispersions, suspensions, emulsions or suspoemulsions. In one
embodiment,
the composition is a ready for use suspension or suspoemulsion.
The average size of the suspended particles is 0.1 to 20, specifically 1.5 to
5 microns
TM
when measured with a laser particle analyzer, e.g a CILAS 920 apparatus.
The viscosity of the aqueous composition is 50 to 2000, more specifically 100
to 1000
TM
mPas when measured with a BROOKFIELD viscometer with spindle 3 at 30 rpm and
25 C.
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
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The aqueous compositions according to the invention are stable and maintain
their
viscosity and homogeneity for at least 12 months at 25 C.
USE
For the purposes of this invention, seed treatments are defined as chemical or
biological
substances that are applied to seeds or vegetative plant propagation materials
to control
disease organisms, insects, or other pests. The seed treatment composition of
the
invention includes neonicotinoid insecticides/acaricides, but can also include
other
pesticides such as bactericides and other classes of insecticides. Most seed
treatments
lo are applied to true seeds, which have a seed coat surrounding an embryo.
However,
some seed treatments can be applied to vegetative plant propagation materials
such as
rhizomes, bulbs, corms or tubers.
The aqueous insecticidal/acaricidal compositions of the invention are
formulated for
protecting cultivated plants and their propagation materials. The inventive
compositions
are advantageously formulated for seed treatment applications against soil
inhabiting
insects, which can damage the crop in the early stages of plant development.
For
example, the compositions can be formulated to target insects and
representatives of
the order Acamia including:
from the order Lepidoptera, for example, Acleris spp., Adoxophyes spp.,
Aegeria spp.,
Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis,
Archips spp.,
Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina
nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis
spp.,
Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis,
Cryptophlebia
leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp.,
Ephestia spp.,
Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita
spp.,
Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia
lycopersicelia, Leucoptera scitella, Lithocollethis spp., Lobesia botrana,
Lymantria spp.,
Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera
spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
Pectinophora
gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella
xylostella, Prays
spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp.,
CA 02567615 2006-11-16
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Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and
Yponomeuta
sPP-;
from the order Coleoptera, for example,
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,
Cosmopolites
spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus
spp.,
Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus
spp.,
Otiorhynchus spp., Phtyctinus spp., Popillia spp., Psylliodes spp.,
Rhizopertha spp.,
Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp.
and
Trogoderma spp.;
1o from the order Orthoptera, for example,
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta
spp.,
Periplaneta spp. and Schistocerca spp.;
from the order isoptera, for example,
Reticulitermes spp.;
from the order Psocoptera, for example,
Liposcelis spp.;
from the order Anoplura, for example,
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and
Phylloxera
spp.;
from the order Mallophaga, for example,
Damalinea spp. and Trichodectes spp.;
from the order Thysanoptera, for example,
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi,
Thrips tabaci and
Scirtothrips aurantii;
from the order Heteroptera, for example,
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster
spp.,
Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella
singularis,
Scotinophara spp. and Triatoma spp.;
from the order Homoptera, for example,
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae,
Aphis spp.,
Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma
larigerum,
Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni,
Lepidosaphes
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spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,
Paratoria spp.,
Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,
Psylla
spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp.,
Saissetia spp.,
Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum,
Trioza
erytreae and Unaspis citri;
from the order Hymenoptera, for example,
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia
polytoma,
Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp.,
Solenopsis
spp. and Vespa spp.;
1o from the order Diptera, for example,
Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala,
Ceratitis
spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila
melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp.,
Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp.,
Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,
Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.
and
Tipula spp.;
from the order Siphonaptera, for example, Ceratophyllus spp. und Xenopsylla
cheopis
and from the order Thysanura, for example, Lepisma saccharina; and
crucifer flea beetles (Phyllotreta spp.), root maggots (Delia spp.), cabbage
seedpod
weevil (Ceutorhynchus spp.) and aphids.
Optionally, in addition to the controll of insect pests, the aqueous
insecticidal
compositions of the invention advantageously are formulated with fungicides
for seed
treatment applications against diseases in the soil, which mostly occur in the
early
stages of plant development. For example, the compositions can be formulated
to target
pathogens including Pythium, Tilletia, Gerlachia, Septoria, Ustilago,
Fusarium,
Rhizoctonia (so-called "damping off complex"); Oomycetes such as Phytophthora,
Plasmopara, Pseudoperonospora, Bremia etc. as well as against the Botrytis
species,
Pyrenophora, Monilinia and further representatives of the Ascomycetes,
Deuteromycetes and Basidiomycetes classes.
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Suitable target crops are especially potatoes, cereals, (wheat, barley, rye,
oats, rice),
maize, sugar beet, cotton, millet varieties such as sorghum, sun flowers,
beans, peas, oil
plants such as rape, canola, soybeans, cabbages, tomatoes, eggplants
(aubergines),
pepper and other vegetables and spices as well as ornamental shrubs and
flowers.
Suitable target crops also include transgenic crop plants of the foregoing
varieties. The
transgenic crop plants used according to the invention are plants, or
propagation
material thereof, which are transformed by means of recombinant DNA technology
in
such a way that they are - for instance - capable of synthesizing selectively
acting toxins
lo as are known, for example, from toxin-producing invertebrates, especially
of the phylum
Arthropoda, as can be obtained from Bacillus thuringiensis strains; or as are
known from
plants, such as lectins; or in the alternative capable of expressing a
herbicidal or
fungicidal resistance. Examples of such toxins, or transgenic plants which are
capable of
synthesizing such loxins, have been disclosed, for example, in EP-A-O 374 753,
WO 93/07278, WO 95/34656, EP-A-0 427 529 and EP-A-451 878.
The inventive compositions are particularly suited for dressing applications
on plant
propagation material. The latter term embraces seeds of all kinds (fruit,
tubers, grains),
cuttings, cut shoots and the like. The preferred field of application is the
treatment of all
kinds of seeds (as specified in the target crops above), and in particular the
seed
treatment of canola, maize, cereals, soybeans and other legumes and crops that
are
susceptible.
The techniques of seed treatment application are well known to those skilled
in the art,
and they may be used readily in the context of the present invention. The
aqueous
neonicotinoid composition of the invention is applied to the seed as slurry or
a soak.
There also may be mentioned, e.g., film coating or encapsulation. The coating
processes are well known in the art, and employ, for seeds, the techniques of
film
coating or encapsulation, or for the other multiplication products, the
techniques of
immersion. Needless to say, the method of application of the inventive
compositions to
the seed may be varied and the invention is intended to include any technique
that is to
be used.
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-20-
A preferred method of applying the aqueous insecticidal composition according
to the
invention consists in spraying or wetting the plant propagation material with
the aqueous
liquid preparation, or mixing the plant material with such liquid preparation.
Also, before
the application, the composition of the invention may be diluted with water by
simple
mixing at ambient temperature in order to prepare an on-farm seed treatment
formulation.
The formulation may be applied at application volumes ranging from 200ml to 3
liters per
to 100 kg seed, more specifically, from 400m1 to 2 liters per 100 kg seed.
As noted above, the compositions of this invention may be formulated or mixed
in the
seed treater tank or combined on the seed by overcoating with other seed
treating
agents. The agents to be mixed with the compounds of this invention may be for
the
control of pests, nutrition, and the control of plant diseases.
The inventive aqueous insecticidal composition has particular application to
concurrent
(such as by slurry) and sequential seed treatments.
2o The aqueous compositions of the invention are both cold and heat stable and
can be
applied to seeds at temperatures ranging from -20 to 40 C.
Seeds treated with the aqueous composition of the invention have a drying time
ranging
from 20 to 60 seconds when being treated at room temperature.
The aqueous neonicotinoid compositions of the invention typically are
distributed in a
storage and shipping system comprising a container ranging in capacity from
about 0. 1
liter to about 2000 liters.
3o For example, the aqueous neonicotinoid compositions of the invention can be
distributed
in small containers, ranging in capacity from about 0. 1 liter to about 10
liters, including
the standard 2.5 gallon (9.46 liter) containers widely used in the United
States, which
typically take the form of jugs or flasks with a replaceable screw-cap. They
are generally
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
-21-
designed for single use and are typically not retumed to the supplier when
empty,
instead being disposed of by the end user in accordance with local
agricultural chemical
container disposal guidelines, procedures, regulations or laws. Commonly, a
plurality of
these small containers are packaged within a single box and a plurality of
such boxes
are shipped on a pallet. During shipment, the small containers (usually within
boxes on
pallets) can be disposed in an enclosed volume such as provided by a rail
boxcar or
road truck, the hold of a ship or aircraft, or a modular box container adapted
for transport
by road, rail and water.
Larger single-use containers, ranging in capacity up to about 200 liters, for
example
about 50 to about 200 liters, are commonly in the form of drums, and can be
shipped in
an enclosed volume as described above, one or more per pallet or unpalleted.
The aqueous neonicotinoid compositions of the invention also can be
distributed in a
large refillable container sometimes known as a bulk or minibulk tank, which
typically
has an integral pump or connector for an external pump to permit transfer of
liquid. Bulk
or minibulk tanks having a capacity of about 200 to about 2000 liters or more
are
typically returned to the supplier when empty and are commonly shipped on a
pallet.
A principal feature of the inventive composition is that it provides a treated
seed with
increased adherence which results in decreased dustiness and the subsequent
elimination of related dust problems. Elimination of the dust associated with
many seed
treatments also eliminates the associated health hazards to those who work
with treated
seeds, such as processing plant employees, truck drivers, warehouse workers,
and
farmers.
Still another advantage of this invention is the uniform coating of-seeds with
non-dusting
seed treatment which will not interfere with germination and sprouting of the
seed but
which will protect the seed and resultant seedling against soil-borne insects
and
representatives of the order acarina.
CA 02567615 2008-02-22
30989-29(S)
-22-
EXAMPLES
In order that those skilled in the art will be better able to practice the
invention, the
following examples are given by way of illustration and not by way of
limitation. In the
following examples, as well as elsewhere in the specification and claims,
temperatures
are in degrees Celsius, the pressure is atmospheric and all parts are by
weight, unless
otherwise clearly indicated. The registered trademarks and other designations
denote
the following products:
Product Composition Source
Surfactants
GeroponTM T77 methyl oleytaurate Na-salt Rhodia
TM
Soprophor 4D384 ethoxylated Tristyrylphenol sulphates Rhodia
TM
Stepan Agent 1411-80A 4E0 nonylphenot/ 6E0 Tallow amine Stepan
TM
Reax 825 ethoxylated lignin sulfonate Westvaco
TM
Genapol X-060 Ethoxylated fatty alcohol Clariant
Polymers
AgrimerTM ST Vinylpyrrolidone/styrene block copolymer ISP
trs
Pluronic P103 EO-PO-EO block copolymer BASF
TM
Pluronic P65 EO-PO-EO block copolymer BASF
TM
Pluronic P108 EO-PO-EO block copolymer BASF
TM
Vinamul 18160 Polyvinylacetate National Starch
.TM
Agrimer 30 Polyvinylpyrrolidone ISP
TM
Agrimer VA 7w Vinylacetate/vinylpyrrolidone copolymer ISP
TM
Agrimer AL 10 Alkylated polyvinylpyrrolidone ISP
PEG 400 Polyethyleneglycol Unichema
TM
Witconol NS 500LO Butanol PO-EO block copolymer Witco
Carriers
VolcalyTM 325mesh Aluminum silicate American Coloid
Auxilaries
Irgalite RedTM C2B Pigment red C2B Ciba Speciality
TM
Antifoam A Silicon oil Dow Corning
CA 02567615 2008-02-22
30989-29(S)
-23-
TM
Proxel GXL Bactericide (1,2-Benzisothiazol-3(2H)-one )
TM
Rhodopol 23 Xanthan gum
Example 1
TM TM
Surfactants (Soprophor 4D384, Reax 835, Stepan Agent 1411-80A), defoaming
agent
TM TM
(Antifoam A) and bactericide (Proxel GXL) are mixed wilh water until a
homogeneous
TM
phase is achieved. Subsequently, Colorant (Irgalite Red C2B), Drying agent
(Ti02),
active ingredients are added and mixed. The resulting mixture is then wet-
milled
through a so-called bead mill (Dyno, Drais, Premier for instance). The milling
parameters are set in such a way that the average particle size of the
resulting ground
premix is within specifications (usually median partical size between 1.5um
and 4.0 um).
TM
Finally, polymer (Pluronic P103) (if any), antifreeze (Glycerine) and
thickening agent
(xantham gum) are added and the final product is mixed for at least 15
minutes.
Aqueous compositions of Examples 2-14 are prepared by following the procedures
given in example 1. The numbers given in the Examples are concentrations in %
weight/weight. All embodiments given below are based on an application volume
of
1500m1 per 100kg of seed. However, the active ingredient concentrations in
each of the
examples given below can be adjusted to application volumes ranging from 200m1
to
3000 ml per 100kg of seed.
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
24
\ ~ \ o 0
0 0 'O
~ T . ~-
~
o n o 0 o e v o
M CO I R N G N ~ ~ CO O O v0
\
0-0 0 0 0 ~ o 0 0
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O N
tV M r ~ ~ M ~ O O O O c~C ~
7
w
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0
U m ~
m T
c m a o 0
o t n
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75 0 ~ Y T
- C
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U v ~~a m'-' -~n 75 O c~a rn
0
w ~
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~ Z N E a>. c 0
co x ~s r> ~ c ea Q~ P m O o o cv
H w U c) -- r c7 a W a w w ZF- 0 F- a w> x m
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
o ~ o o ~ r ~
o ao u~ ~ o o a o
!f) C') ~ r- O CV C+) O O cG
.,0 o o ,0 o 0 0 ~ o 0 0
O ~ N T \ ~ 0-0 ~ O
tf cq CV 0 t6
m
~
.U
=3
~
(a
m
U
Q
.. p m C
E O
C c m ~
p n Q 75 o
c_ m n 2= 0 Q
Z Z'
Y T
~ ~ 0 U C
0
p z
a m C7 F' "0 o m -m
~ 7
V N m T m m p m ~ n 0 f 01
T
a~ n a a o c u ~i p~~
E m"- o'd cmi Q. a o: z N~. o E a L o m
t'~ w LU = ~- t~ a n a w w z~ c~ -'~ a w> x m~
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
26
-0
O ton N 0-0 O o 0 0-0 O N 0-0 0 0 o N17 '~0 O
N - in - N N ~ O tf) CV N - O O c0
0 ~ o 0 0 0 O O
Cp ~ ~ \
Of C , ~ ~ ~ ~ N , , , N 0 0 t6
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O O
~ o ~ 0-0 ~ ~ tn O N U O
a0 N O , m , N , , N cf)
o o \ \ o 0 0
O N o 0 0 V) 7 ~-o N ~ O y
N
C
o o 0-* o 0 0-0
O O
\ N \ , N
~O N O O ~ ~ ~ N ~ C cl) C O c-o o
:2
~
0
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f~
'0
E G)
j O
O C , ~
C m
O N O O
o. ~
C n ~
~ O y m ~vC =i.
E N T N L C C ~ ~
'
0 N O M N 7
p 0
V -~ a ~ N V p 7 0 16 O
= o r X c m cs 0 "S. o W E
~~ co E m> r N~ o rn a~ m
-
i ' a o Z N>+ o E >
,, c
w m
~ a) H C7 a in a w w z~ U~ a w> x
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
27
~ o ~ a 'O \ O o
ao o ~ ~ ~
~ N 0 O CV ~ N . . . N C9 0 0 N ~
~
m
=U
C
3 0 0 0 0 0 0 0 0 N ~ O
=O
O r N 0 r 0 ~ fV ~ ~ O ~ oV . ~ C O t0 o
x
0
m
E
cd m
L m C
j
=.=. C o.
~ U
- v0 OT.
~ m Z. _> m ~c >.
~ m U 5,m
O
p ~ p =C
E ~ N F- =O O m. O L N 7
m V 0 i ~
0 C C ~
fd .~.. m m c~6 O= W E
? a m ox o c a~ m as a~ oc ro O a
E E a C m coi cmi a Q. o w Z ) c~ >, o E a c m
n 2 ~' m>. o a L = Q co ~ rn p c m o cu
F ~ j ~ U. p~ ~ C'} n. cn a. w w z}- U H n w > x m
CA 02567615 2006-11-16
WO 2006/024333 PCT/EP2005/006844
-28-
Example 13
In a manner consistent with the process described above in Example 1, the
following
active ingredients are combined with surfactants, solid carriers, antifreeze
agents and
other auxiliaries as set forth in this invention to form an aqueous
composition. The
numbers given are concentrations in % weight/weight.
18% to about 27 % Thiamethoxam
0.5% to about 2% Fludioxonil
0.5% to about 2% Mefenoxam
0.1 % to about 1% Azoxystrobin
Water, to 100%
Example 14
In a manner consistent with the process described above in Example 1, the
following
active ingredients are combined with surfactants, solid carriers, antifreeze
agents and
other auxiliaries as set forth in this invention to form an aqueous
composition. The
numbers given are concentrations in % weight/weight.
Clothianidin 20-30% Thiram 5-10%
Mefenoxam 0.05-2% Carboxin 1-5%
Water to 100%
Although the foregoing invention has been described in some detail by way of
illustration
and example for purposes of clarity of understanding, it will be apparent that
various
changes and modifications may be practiced within the scope of the appended
claims.
