Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
FERTILIZER COMPATIBLE EMULSIFIABLE CONCENTRATES
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This
application claims the benefit of U.S. Provisional Application No.
62/106,044, which was filed January 21, 2015, and is hereby incorporated by
reference in
its entirety for all that it teaches.
FIELD OF THE INVENTION
[0002] The
present invention relates generally to emulsifiable pesticide
concentrates, and more particularly to emulsifiable pesticide concentrates
that uniquely
contain water and are compatible with strong electrolyte solutions such as
starter
fertilizers.
BACKGROUND OF THE INVENTION
[0003] Many
direct seeded crops suffer from pests that reside in the soil. For
example, wheat seeds are often treated with insecticide for protection from
attack (Pike,
et al. Compatibility of Imidicloprid with Fungicides as a Seed-Treatment
Control of
Russian Wheat Aphid (Homoptera: Aphididae) and Effect on Germination, Growth
and
Yield of Wheat and Barley. J ECONOMIC ENTOMOLOGY, 86(2): 586-593 (1993)).
Separately, maize is often planted with a soil insecticide as an aqueous
solution applied
into the furrow as the seeds are deposited in the soil. In areas infested with
the pests
1
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
described as corn rootworms, application of a soil insecticide often results
in significantly
improved plant growth and resulting increased yields (Sutter, et al. Effect of
Insecticide
Treatments on Root Lodging and Yields of Maize in Controlled Infestations of
Western
Corn Rootworm (Coleoptera: Chry som el i dae). J ECONOMIC ENTOMOLOGY, 83(6):
2414-
2420 (1990)).
[0004]
Alternatively, genetically modified maize has unique traits that control
corn rootworn including production of toxins in the roots that control corn
rootworms
(Tabashnik & Gould. Delaying Corn Rootworm Resistance to Bt Corn. J ECONOMIC
ENTOMOLOGY, 105(3): 767-776 (2012)) Widespread use of these traits resulted in
reduced use of soil applied insecticides since the commercial introduction of
the trait
(Brookes & Barfoot. Global impact of biotech crops: Socio-economic and
environmental
effects in the first ten years of commercial use. AoBioFoRum, 9(3), 139-151
(2006);
Benbrook. Impacts of genetically engineered crops on pesticide use in the U.S.
-- the first
sixteen years. ENVIRONMENTAL SCIENCES EUROPE, 24:24 (2012)). Unfortunately,
this
widespread use has resulted in scattered reports of corn rootworm resistance
to the
genetic traits (Gassmann, et al. Field-Evolved Resistance to Bt Corn by
Western Corn
Rootworm. PLoS ONE, 6(7):e22629, doi:10.1371/journal.pone.0022629 (July 29,
2011)).
As a result of this resistance, soil applied maize insecticide use is
increasing to control the
populations of corn rootworm no longer susceptible to the genetic traits
(Brooks. Soil
Insecticide Use in Corn to Top 15 Million Acres. AGWEB.COM, (Feb. 15, 2013)).
[0005] In
parallel with the adoption of the genetic traits to control corn
rootworm, the practice of applying "starter fertilizer" increased in the
period 2000-2013.
The purpose of starter fertilizer is to promote early season seedling growth
which results
2
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
in stronger plants with higher yield potential (Vetsch & Randall. Corn
Production as
Affected by Tillage System and Starter Fertilizer. AGRONOMY JOURNAL, 94(3):
532-540
(2002)). Fertilizers are typically designated by a numerical code with the
first number
representing the % nitrogen, the second number the % phosphorous, and the
third number
the % potassium. Additional numbers may be included in the formula with a
letter
signifying the nutrient elements included, such as S for sulfur or Zn for
zinc. A common
starter fertilizer is known as 10-34-0, which contains 10% nitrogen, 34%
phosphorous,
and 0% potassium. Other fertilizers are available with different blends of
nitrogen,
phosphorous, and potassium, including, for example, 7-21-7, 25-30-0, 3-18-18,
7-17-3,
18-13-0-7S, 5-0-20-13S, 10-0-0-10Zn, and 9-10-24. Starter fertilizers are very
strong
electrolyte solutions with high percentages of dissolved solids.
[0006] One
formulation type of soil insecticides is described as emulsifiable
concentrates (typically abbreviated as EC). These formulations are popular
because they
are economical and effective. An EC is typically composed of an active
ingredient
(insecticide) dissolved in a water immiscible solvent, often derived from
petroleum, and a
mixture of surfactants that are added to act as an emulsifier (The University
of Arizona,
College of Agriculture and Life Sciences. Chapter 3: Pesticide Types &
Formulations.
ARIZONA AGRICULTURAL PESTICIDE APPLICATOR TRAINING MANUAL. (2000)). This type
of formulation is called a concentrate because it is designed to be diluted in
water prior to
use to deliver the proper insecticide dose. For example, an EC may contain 1
to 5 pounds
of insecticide active ingredient per gallon and is intended to be diluted in
water before
spraying. When the mixture is added to water in a farmer's mix tank, an
emulsion of
finely dispersed solvent droplets (in which the insecticide is dissolved)
forms with a
3
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
typical white, milky appearance. The emulsion may quickly separate into water
and oil
phases (oil floating on top of water), which is referred to as an emulsion
failure (U.S. Pat.
No. 5,834,400 to Narayanan & Goehner), or, preferably, the emulsion may remain
stable
and dispersed for hours¨and in some cases days or weeks.
[0007] A
related type of emulsified product is known as an emulsion in water,
abbreviated EW (also referred to as a concentrated emulsion or CE
formulation), where a
manufacturing concentrate is pre-mixed with water and sold as a stable
emulsion which
can then be diluted. One drawback to EW formulations is they can develop high
viscosity and be difficult to pour. A further related formulation type is
known as a
microemulsion or ME. This formulation type typically contains high levels of
surfactants, forms a stable, clear solution when produced, and, upon dilution
in water,
produces a clear solution.
[0008] Of the
types of emulsified products, EC products greatly outnumber
EW products in the market place because of their economical nature and the
many kinds
of pesticides that are amenable to being formulated as an EC.
[0009]
Emulsion stability is an important property of an EC and can be
impacted by the nature of the active ingredient, the type and amount of
solvent, and the
type and amount of emulsifier in the formulation. Sometimes an emulsion can be
very
stable in water, which has low ionic strength (for example 34 ppm dissolved
solids) but
unstable in high ionic strength water (e.g., 1000 ppm dissolved solids). The
quality of an
emulsion is important for pesticide performance and as such, there are
standard test
methods for assessing the stability of a particular product (see, e.g., ASTM
Method
4
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
E1116-98; see also CIPAC Method MT 36). The ability to remain stable in high
ionic
strength aqueous solutions becomes a critical factor when an EC insecticide
(such as the
insecticide bifenthrin) is added to a tank containing an aqueous-based starter
fertilizer,
such as 10-34-0. Typical ECs of bifenthrin separate immediately when added to
10-34-0
due to the high ionic strength.
[0010] There
are at least two prior methods to overcome this incompatibility
of pesticide formulations in liquid fertilizers. For example Cummings (U.S.
Pat. No.
4,304,587) teaches the addition of attapulgite clay to liquid fertilizer prior
to addition of
an organophosphate EC insecticide. The fertilizer plus clay addition allows
for a stable
emulsion to form in the final combined solution. In this application,
unfortunately, the
clay cannot be added to the EC formulation and must be added separately to the
mixture,
creating handling and mixing problems at the user level. In U.S. Patent No.
8,263,527 to
Martin, attapulgite clay is also used, but in this case it is added to a
suspension
concentrate (SC) formulation of the pyrethroid insecticide bifenthrin. The
SC
formulation forms a stable suspension in liquid fertilizer without separation
in a two (2)
hour time period. In both cases above, the formulation must be added to cold
water, as
the in-furrow planting/fertilizer application occurs early in the growing
season and spray
water is typically cold in this part of the season. SC formulations can suffer
from high
viscosity and poor dispersion in cold water, again causing handling and mixing
problems
for the user.
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
SUMMARY OF THE INVENTION
[0011] It is
an object of this invention to supply an EC formulation that is
readily and easily emulsified into an aqueous-based fertilizer, especially
starter fertilizers,
and that typically does not separate into oil and water phases for a minimum
of one hour
in a standard laboratory test. It is another object of this invention to
supply an EC
formulation that is readily and easily emulsified into an aqueous-based
fertilizer,
especially starter fertilizers, and that typically does not separate into oil
and water phases
for a minimum of one hour in field-use conditions (tank mix and application
tank). It is a
further object of this invention to supply an adjuvant composition formulation
that is
readily and easily mixed with a water immiscible pesticide in an aqueous-based
fertilizer,
especially starter fertilizers, to form an emulsion, and that typically does
not separate into
oil and water phases for a minimum of one hour in field-use conditions (tank
mix and
application tank).
[0012] It is
another object of this invention to provide compositions for
controlling soil pests, such as insects or fungi, which are capable of forming
a stable
emulsion in an aqueous-based fertilizer, especially starter fertilizers, and
then delivering
this stable emulsion to the target soil, seed, seedling, or plant (treatment
target) via useful
application methods such as sprays or in-furrow application. The compositions
of this
invention use a surfactant blend which contains an alkylpolyglucoside (APG)
surfactant
and, optionally, an alcohol ethoxylate and/or other co-surfactants. Minor
amounts of
other formulants are included to stabilize the surfactant blend, including,
but not limited
to, glycol and methyl ester solvents for low temperature stability and cold
water
mixability, organic acids to adjust pH to ensure chemical stability of the
active
6
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
ingredient, defoamers, and/or preservatives. No attapulgite, montmorillonite,
or kaolin
clays are used in this invention.
[0013] It is a
further object of this invention to provide methods for
controlling soil pests, such as insects or fungi, by providing a composition
capable of
forming a stable emulsion in an aqueous-based fertilizer, especially starter
fertilizers, and
delivering this stable emulsion to the target soil, seed, seedling, or plant
(treatment target)
via useful application methods such as sprays or in-furrow application.
DETAILED DESCRIPTION
[0014] The
following detailed description is presented to enable any person
skilled in the art to make and use the invention. For purposes of explanation,
specific
details are set forth to provide a thorough understanding of the present
invention.
However, it will be apparent to one skilled in the art that these specific
details are not
required to practice the invention. Descriptions of specific applications are
provided only
as representative examples. Various modifications to the preferred embodiments
will be
readily apparent to one skilled in the art, and the general principles defined
herein may be
applied to other embodiments and applications without departing from the scope
of the
invention. The present invention is not intended to be limited to the
embodiments shown,
but is to be accorded the widest possible scope consistent with the principles
and features
disclosed herein.
[0015] We have surprising discovered EC (emulsified concentrate)
formulations that allow for an EC pesticide composition to be readily and
easily
emulsified into an aqueous-based starter fertilizer and that typically does
not separate into
7
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
oil and water phases for a minimum of one hour in a standard laboratory test.
Even more
surprising, is the discovery that the EC formula can contain from 5% to up to
25% water
by total weight without forming an "emulsion in the can," and remains
transparent and
free flowing. It is this property that makes this novel EC formulation
discovery different
from conventional EC (which contain no water) and EW (which are milky
emulsions in
the can) formulations. We have also discovered that the adjuvant composition
formulations can be mixed with the water immiscible pesticide in an
application ready
composition, i.e., a tank mix, that have beneficial emulsion properties.
[0016] The EC
and adjuvant formulation compositions of this invention use a
surfactant blend which contains an alkylpolyglucoside (APG) surfactant (e.g.,
AGNIQUE PG 8105, BASF Corporation, Cincinnati, OH) and, optionally, an
alcohol
ethoxylate (such as ECOSURFTM EH-6, Dow Chemical, Midland, MI) and/or other co-
surfactant(s). Minor amounts of other formulants are included to stabilize the
physical
properties of the final product blend, including, but not limited to, glycol
and methyl ester
solvents for low temperature stability and cold water mixability, organic
acids to adjust
pH to ensure chemical stability of the active ingredient, defoamers, and/or
preservatives.
Use of one or more of these optional additional other formulants may depend on
the
desired properties of the final product blend and environmental factors (such
as climate
and geography of the intended application site). No attapulgite,
montmorillonite, or
kaolin clays are used in this invention.
[0017] APG
surfactants are known in the art as being both tolerant of high
electrolyte solutions (such as aqueous-based starter fertilizers) and being
hydrotropes. A
hydrotrope is a compound that solubilizes hydrophobic compounds in aqueous
solutions.
8
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
Typically, hydrotropes consist of a hydrophilic part and a hydrophobic part,
but the
hydrophobic part is generally too weak functionally to cause spontaneous
aggregation or
micelle formation. Hydrotropes do not have a critical concentration above
which self-
aggregation "suddenly" starts to occur¨as found for micelle- and vesicle-
forming
surfactants, which have a critical micelle concentration (cmc).
[0018] The
preferred commercial form of the APG used in the present EC and
adjuvants formulations (AGNIQUE PG 8105) is sold containing 40% by weight of
water, and other common APG products also contain from 40% to 50% water.
Consequently, using an APG in an EC formulation is fraught with difficulty, as
the water
in the surfactant is not soluble with the water immiscible solvent, resulting
in
incompatibility and poor physical stability of the formulation as evidenced by
phase
separation into solvent and water layers upon standing. Therefore, APG alone
will not
function as the sole surfactant in the formulations of this discovery.
Additional
surfactants and/or formulants can be used to assist the APG. For example, a
straight or
branched chain alcohol ethoxylate can be used in the surfactant blend as a co-
surfactant.
Other co-surfactants capable of stabilizing the formulation with water and APG
can be
used in addition to or in place of an alcohol ethoxylate.
[0019] As
mentioned above, other auxiliary formulants can be added to
ensure long term storage stability and user acceptability, including, but not
limited to,
glycol and methyl ester solvents for low temperature stability and cold water
mixability,
organic acids to adjust pH to ensure chemical stability of the active
ingredient,
defoamers, and/or preservatives. No attapulgite, montmorillonite, or kaolin
clays are
used in the novel EC or adjuvant formulations.
9
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
[0020] The
above formulation compositions are well suited to be directly
added to an aqueous-based fertilizer, especially starter fertilizers, in a
mixing or treatment
tank without further dilution, if desired by the user. Alternatively, the
adjuvant
formulation composition can be mixed together with the fertilizer and the
water
immiscible pesticide in the tank. In the tank a stable emulsion will form,
allowing for
consistent application of the pesticide via in-furrow dribble or injection,
direct application
to soil via shanking or spraying, or chemigation via irrigation systems.
Depending on the
pesticide and the pest involved, any or all of these applications methods may
be used.
[0021] Here we
provide further details of our EC and adjuvant formulation
compositions and methods for control of soil-borne pests when the formulated
pesticides
are applied to the soil with an aqueous-based fertilizer, such as the liquid
"starter
fertilizer" 10-34-0 (ammonium polyphosphate solution) or other aqueous-based
starter
fertilizers with different N-P-K (nitrogen-phosphorous-potassium) amounts.
[0022] It has
been surprisingly discovered that a water-containing surfactant,
such as alkylpolyglucosides (APG) plus co-surfactant, can be incorporated into
an EC
pesticide formulation consisting of a water immiscible solvent system and
pesticide
without forming an emulsion, resulting in a clear, stable solution. The "on-
board" water
neither turns the EC compositions cloudy nor increases the viscosity of the
system like
concentrated emulsions (CE, also called EW) do. The lack of viscosity increase
is
particularly useful when the product is deployed in cold water for early
season
application. Suitable alkylpolyglucosides include AGNIQUE (ID PG 8105, AGNIQUE
(ID
PG 8107 and AGNIQUE (ID PG 9116 (all available from BASF in Cincinnati, OH).
Preferably, the APG is AGNIQUE (ID PG 8105. Other alkylpolyglucosides can also
be
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
used, if the desired EC properties discussed herein remain in the final EC
pesticide
formulation.
[0023] The
alkylpolyglucosides (APG) preferably comprises a carbon chain
length of 6 to 18, but other carbon chain lengths for APG may be acceptable
and
considered to be within the scope and spirit of the present invention. The
alkylpolyglucosides (APG) is present in the concentrate composition
formulations in
from 10 to 70% by weight. Preferably, the alkylpolyglucosides (APG) is present
in the
concentrate composition formulations in from 25 to 70% by weight. More
preferably, the
alkylpolyglucosides (APG) is present in the concentrate composition
formulations in
from 40 to 60% by weight.
[0024] At
least one non-ionic co-surfactant is also included in the EC
formulations of the present invention and is selected from one or more of the
following
groups: straight chain alcohol ethoxylates (e.g., AGNIQUE IDA-6, BASF,
Cincinnati
OH); branched chain alcohol ethoxylates (ECOSURFTM EH-6, Dow, Midland MI;
LUTENSOL XP-80, BASF, Cincinnati, OH); alkylaryl ethoxylates (TERGITOL NP-
9, Dow, Midland, MI); castor oil ethoxylates or other alkoxylated
triglycerides
(AGNIQUE CSO-36, CASO-25, and CSO-16, BASF, Cincinnati, OH); sorbitan esters
and sorbitan ester ethoxylates (AGNIQUE SMO, AGNIQUE STO, AGNIQUE
SMO-20, or AGNIQUE STO-20, BASF, Cincinnati, OH); fatty acid polyethylene
glycol esters (AGNIQUE PEG 400 DO, BASF, Cincinnati OH), ethylene-propylene
block co-polymers (PLURONIC P-104, BASF, Cincinnati, OH), alkylbenzene
sulfonates, alkyl naphthalene sulfonates, naphthalene sulfonate condensates,
alkanolamides, alkylphenol ethoxylates, betaines, amine oxides, ethoxylated
fatty amines,
11
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
fatty alcohols, fatty acid PEG (polyethyleneglycol) esters, ethoxylated fatty
acids,
glycerol and polyglycerol esters, polyol esters, phosphate esters, sulfates,
sulfosuccinates,
ether sulfates, diphenyl sufonates, ethylene oxide-propylene oxide block co-
polymers,
acrylic copolymers, taurates, sarcosinates, iminopropionates, and combinations
thereof
Named examples in the list above are provided as examples only, and are not
meant to be
limiting in any way.
[0025] The
water immiscible solvent system for dissolving a water insoluble
pesticide may contain a water immiscible solvent selected from light or heavy
aromatic
solvents, linear or branched paraffinic oils, dimethylamides, alkyl esters,
aromatic esters,
alkyl substituted pyrrolidones, glycerol esters, fatty alcohols, ethoxylated
methyl esters,
long chain aliphatic hydrocarbons, vegetable oils, terpene-based solvents
(such as,
without limitation, turpentine, d-limonene, and pine oils), and combinations
thereof.
[0026] In some
embodiments the pesticide active ingredient of the novel EC
formulations of the present invention is an insecticide. Suitable insecticide
active
ingredients for use in the novel EC formulations of the present invention
include 1,2-
dichloropropane, abamectin (avermectins), acephate, acetamiprid, acethion,
acetoprole,
acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin,
allethrins, allosamidin,
allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion,
aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion,
azadirachtin,
azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium
hexafluorosilicate,
barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-
cypermethrin,
bifenthrin, BIOALLETHRIN , bioethanomethrin, biopermethrin, bistrifluron,
borax,
boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,
12
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,
butoxycarboxim,
cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate,
carbaryl,
carbofuran, carbon disulfide, carbon tetrachloride, carb ophenothi on,
carbosulfan, cartap,
cartap hydrochloride, chlorantraniliprole, chl orb i cy cl en, chlordane,
chlordec one,
chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr,
chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin,
chlorphoxim,
chlorprazophos, chlorpyrifos, chl orpyrifo s-m ethyl, chlorthiophos, chrom
afenozi de,
cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel,
clothianidin, copper
acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos,
coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos,
cyanophos,
cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin,
cyhalothrin,
cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran,
deltamethrin,
demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,
dem eton-O-methyl, dem eton- S, dem
eton- S-m ethyl, dem eton- S-m ethyl sulphon,
di afenthiuron, di alifo s, diatomaceous earth, di azinon, di capthon, di chl
ofenthi on,
di chl orvo s, di cresyl, di crotoph o s, di cy cl anil, di el drin,
diflubenzuron, dil or, dimefluthrin,
dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex,
dinex-
di cl exine, dinoprop, dinosam, dinotefuran, di ofenol an, di oxab enzofo s,
di oxac arb,
dioxathion, di sulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-
potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin
benzoate,
EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,
eprinomectin,
esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole,
ethoate-methyl,
ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene
dichloride,
13
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,
fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim,
fenoxycarb,
fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl,
fenvalerate, fipronil,
flonicamid, flubendiamide (additionally resolved isomers thereof), flucofuron,
flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox,
fluvalinate, fonofos,
formetanate, formetanate hydrochloride, formothion, formparanate, formparanate
hydrochloride, fosmethilan, fospirate, fosthietan, fufenozide, furathiocarb,
furethrin,
gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor,
heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide,
hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane,
IPSP,
i sazofos, i sob enzan, i socarbophos, i sodrin, i sofenphos, i sofenphos-
methyl, i soprocarb,
isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II,
jodfenphos,
juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,
kinoprene,
lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos,
lufenuron,
lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon,
meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone,
methacrifos, methamidophos, methidathion, methiocarb, methocrotophos,
methomyl,
methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl
i sothiocyanate, methyl chloroform, methylene chloride, metofluthrin,
metolcarb,
metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox,
mirex, monocrotophos, monomehypo, monosultap, morphothion, moxidectin,
naftalofos,
naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine,
nitrilacarb, novaluron,
noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos,
oxydisulfoton,
14
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
para-dichlorobenzene, parathion, parathion-methyl, penfluron,
pentachlorophenol,
permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,
phosmet,
phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos,
pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium
thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III,
primidophos,
profenofos, profluralin, profluthrin, promacyl, promecarb, propaphos,
propetamphos,
propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,
pyraclofos,
pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,
pyridaben,
pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate,
pyriprole,
pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,
resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen,
silica gel,
sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium
thiocyanate,
sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron,
sulcofuron-
sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-
fluvalinate,
tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron,
tefluthrin,
temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos,
tetramethrin,
tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos,
thiocarboxime, thi ocy clam, thi ocy cl am oxalate, thiodicarb, thiofanox,
thiometon,
thiosultap, thiosultap-di sodium, thi o sultap-mono s odium, thuringiensin,
tolfenpyrad,
tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate,
triazophos,
trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron,
trimethacarb,
triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin,
zolaprofos, and
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
combinations thereof (collectively these commonly named insecticides are
defined as the
"Insecticide Group").
[0027] In
preferred embodiments, the insecticide is selected from the group
consisting of bifenthrin, cypermethrin, deltamethrin, esfenvalerate,
imidacloprid, lambda-
cyhalothrin, permethrin, pyrethrins, tebupirimphos, terbufos, tefluthrin,
chlorethoxyfos,
dichlorvos, phorate, dicrotophos, and combinations thereof. In more
preferred
embodiments, the insecticide is selected from the group consisting of
bifenthrin,
tebupirimphos, terbufos, tefluthrin, chlorethoxyfos, dichlorvos, and
combinations thereof
In further preferred embodiments, the insecticide is bifenthrin.
[0028] In some
embodiments the pesticide active ingredient of the novel EC
formulations of the present invention is a fungicide. Suitable fungicide
active ingredients
for use in the novel EC formulations of the present invention include (3-
ethoxypropyl)mercury bromide, 2-methoxyethylmercury chloride, 2-phenylphenol,
8-
hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, acibenzolar,
acibenzolar-S-
methyl, acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol,
ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin, azaconazole,
azithiram,
azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl,
benquinox, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl,
benzalkonium
chloride, benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid,
bethoxazin, binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-
S, Bordeaux
mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate,
butylamine, calcium polysulfide, captafol, captan, carbamorph, carbendazim,
carboxin,
carpropamid, carvone, C he shunt mixture, chinomethionat, chlobenthiazone,
16
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalenes,
chloroneb,
chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climb azol e,
clotrimazole, copper
acetate, copper carbonate basic, copper hydroxide, copper naphthenate, copper
oleate,
copper oxychloride, copper silicate, copper sulfate, copper zinc chromate,
cresol,
cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide,
cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, dazomet,
dazomet-
sodium, DBCP, debacarb, decafentin, dehydroacetic acid, dichlofluanid,
dichlone,
dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,
diclomezine-sodium,
di cl oran, di ethofencarb, diethyl pyrocarbonate, difenoconazole,
diflumetorim,
dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,
dinobuton,
dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon,
diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, DNOC-
ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate,
dodemorph benzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos,
epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,
ethylmercury 2,3-
dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide,
ethylmercury
chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone,
fenaminosulf,
fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan,
fenoxanil,
fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin chloride, fentin
hydroxide, ferbam,
ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluopicolide,
fluopyram,
fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,
flusulfamide,
flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, formaldehyde,
fosetyl, fosetyl-
aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole,
furconazole-cis,
17
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
furfural, furmecyclox, furophanate, glyodin, griseofulvin, guazatine,
halacrinate,
hexachlorobenzene, hexachlorobutadiene, hexaconazole, hexylthiofos,
hydrargaphen,
hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole,
iminoctadine,
iminoctadine triacetate, iminoctadine trialbesilate, iodomethane, ipconazole,
iprobenfos,
iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, isovaledione,
kasugamycin,
kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil,
mecarbinzid,
mepanipyrim, mepronil, meptyldinocap, mercuric chloride, mercuric oxide,
mercurous
chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium,
metam-
sodium, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide,
methyl i sothiocyanate, methylmercury benzoate, methylmercury di cy andi ami
de,
methylmercury p entachl orophenoxi de, metiram, metominostrobin, metrafenone,
metsulfovax, milneb, my cl obutanil,
myclozolin, N-(ethylmercury)-p-
toluenesulphonanilide, nabam, natamycin, nitrostyrene, nitrothal-isopropyl,
nuarimol,
OCH, octhilinone, ofurace, orysastrobin, oxadixyl, oxine-copper, oxpoconazole,
oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole, pencycuron,
penflufen,
pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercury acetate,
phenylmercury chloride, phenylmercury derivative of pyrocatechol,
phenylmercury
nitrate, phenylmercury salicylate, phosdiphen, phthalide, picoxystrobin,
piperalin,
polycarbamate, polyoxins, polyoxorim, polyoxorim-zinc, potassium azide,
potassium
polysulfide, potassium thiocyanate, probenazole, prochloraz, procymidone,
propamocarb,
propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothiocarb,
prothiocarb hydrochloride, prothioconazole,
pyracarbolid, pyraclostrobin,
pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril,
pyrifenox,
18
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
pyrimethanil, pyriofenone, pyroquilon, pyroxychlor, pyroxyfur, quinacetol,
quinacetol
sulfate, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole,
salicylanilide,
sedaxane, silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide,
sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, streptomycin,
sulfur,
sultropen, TCMTB, tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram,
tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide,
thiochlorfenphim,
thiomersal, thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil,
tioxymid,
tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,
triadimenol, triamiphos,
triarimol, triazbutil, triazoxide, tributyltin oxide, trichlamide,
tricyclazole, tridemorph,
trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole,
uniconazole-P,
validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate, zineb,
ziram,
zoxamide, and combinations thereof (collectively these commonly named
fungicides are
defined as the "Fungicide Group").
[0029] In
preferred embodiments, the fungicide is selected from the group
consisting of propiconazole, prothioconazole, metconazole, tebuconazole,
pyraclostrobin,
trifloxystrobin, azoxystrobin, and combinations thereof. In more preferred
embodiments,
the fungicide is selected from the group consisting of propiconazole,
tebuconazole,
prothioconazole, pyraclostrobin, and trifloxystrobin, and combinations
thereof. In further
more preferred embodiments, the fungicide is propiconazole.
[0030] In some
embodiments the pesticide active ingredient of the novel EC
formulations of the present invention is a fatty acid, dicarboxylic acid,
fatty acid salt, or
derivatives thereof. Suitable fatty acid and dicarboxylic acid active
ingredients for use in
the novel EC formulations of the present invention include fatty acids from C3
to C22 in
19
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
carbon chain length and dicarboxylic acids from C2 to C18. In preferred
embodiments,
the carbon chain length is C8, C9, and C10. Collectively, these fatty acid,
dicarboxylic
acid, fatty acid salt, or derivatives thereof are defined as the "Fatty Acid
Group."
[0031] In
another embodiment the formulation may contain water insoluble
herbicides including (2,4-dichlorophenoxy)acetic acid (2,4-D) esters and non-
auxin
herbicides. Representative examples of non-auxin herbicides include acetyl CoA
carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors,
acetohydroxy
acid synthase (AHAS) inhibitors, photosystem II inhibitors, protoporphyrinogen
oxidase
(PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl
shikimate-3-
phosphate (EPSP) synthase inhibitor, glutamine synthetase inhibitor,
dihydropteroate
synthetase inhibitor, mitosis inhibitors, and nucleic acid inhibitors; salts
and esters
thereof; racemic mixtures and resolved isomers thereof; and combinations
thereof
(collectively, these commonly named herbicides and the following
representative
examples are defined as the "Herbicide Group.").
[0032]
Representative examples of ACCase inhibitors include clethodim,
clodinafop, fenoxaprop-P, fluazifop-P, quizalofop-P, and sethoxydim.
[0033]
Representative examples of ALS or AHAS inhibitors include
flumetsulam, imazamethabenz-m, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, metsulfuron, prosulfuron, and sulfosulfuron.
[0034]
Representative examples of photosystem II inhibitors include atrazine,
cyanazine, diuron, and metibuzin.
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
[0035] Representative examples of PPO inhibitors include acifluorofen,
butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, fluthiacet, flumiclorac,
flumioxazin,
fomesafen, lactofen, oxadiazon, oxyfluorofen, and sulfentrazone.
[0036] Representative examples of carotenoid biosynthesis inhibitors
include
aclonifen, amitrole, diflufenican, mesotrione, and sulcotrione.
[0037] A representative example of a dihydropteroate synthetase
inhibitor is
asulam.
[0038] Representative examples of mitosis inhibitors include
acetochlor,
alachlor, dithiopyr, S-metolachlor, and thiazopyr.
[0039] Representative examples of nucleic acid inhibitors include
difenzoquat, fosamine, metham, and pelargonic acid.
[0040] In another embodiment, the concentrate composition formulations
of
the present invention may be diluted to a working dilution strength aqueous-
based
composition for application. The aqueous-based solution may comprise any water
solution. Preferably, the aqueous-based solution is an aqueous-based starter
fertilizers.
Representative aqueous-based starter fertilizers include (X-Y-Z-A-B, where X =
nitrogen
content by percent weight, Y = phosphorus content by percent weight, Z =
potassium
content by percent weight, and A & B may be other fertilizer elements such as
sulfur,
zinc, manganese, iron, boron, copper, and other micronutrients) 10-34-0, 7-21-
7, 25-30-0,
3-18-18, 7-17-3, 18-13-0-7S, 5-0-20-13S, and 10-0-0-10Zn. Many other aqueous-
based
21
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
starter fertilizers are possible depending on the formulation and starting
materials used
and this list is not intended to be all inclusive.
EXAMPLES
[0041] The
following non-limiting examples are provided to illustrate the
utility of the present invention. For ease of production, the surfactant blend
was prepared
separately and then used to prepare the formulated pesticide. This order is
not required,
and the finished pesticide can be prepared by adding the individual components
in a
blender.
TABLE 1 ¨ Example 1 Surfactant Blend (by weight, total)
Alkylpolyglucoside 58.70
ECOSURFTM EH-6 30.19
Hexylene Glycol 4.6
Capric/Caprylic Methyl Ester 4.6
Citric Acid 1.82
Preservative 0.09
TABLE 2 ¨ Example 1 Formulated Product (by weight, total)
Heavy Aromatic Solvent 29.0
Technical Bifenthrin (98.1% purity) 17.5
Example 1 Surfactant Blend 54.5
[0042] The
formulated product contains 13.14% water based on the
commercial APG product in the surfactant blend and the aqueous citric acid
containing
22
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
water. The formulated product is a clear, yellow liquid with low viscosity
(e.g., <100
centipoise) at room temperature. No milkiness or other sign of emulsion
formation is
present. This product is physically stable at 4 C, 25 C and 50 C for 30
days with no
phase separation or crystal growth.
TABLE 3 ¨ Example 2 ¨ Single blend
Propiconazole Technical (95% purity) 18.05
Alkylpolyglucoside 52
ECOSURFTM EH-6 16.45
Aromatic 150 Solvent 10
Hexylene Glycol 2.5
Citric Acid (50% aqueous solution) 1
[0043] This
formulation contains 21.3% water based on the water in the
commercial alkylpolyglucoside and citric acid. The product is a clear, yellow
liquid with
a viscosity of < 100 centipoise.
[0044] Upon
dilution in water or in 10-34-0 fertilizer a cloudy emulsion forms
which is stable for at least two hours with no phase separation.
[0045] As
shown in Example 2, a single blend of all the ingredients will form
a clear, stable EC containing water.
[0046] The
utility of producing the EC in either two parts (as in Example 1) or
in one part (Example 2) gives the maximum flexibility to the producer for how
to
23
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
manufacture the formulation compositions of this invention depending on
specific plant
equipment.
[0047] TABLE 4 ¨ Summary of Formulation Types Showing Unique
Properties of the Present Invention:
Formulation Appearance Appearance Viscosity Viscosity Contains
(neat) (diluted) (neat) (diluted) water
Emulsifiable Clear Milky white Low Low NO
Concentrate
(EC)
Concentrated Milky white Milky white High Low YES
Emulsion (CE
or EW)
Mi croemul si on Clear Clear Low Low YES
(ME)
Present Clear Milky White Low Low YES
Invention
(Aqueous EC
or AEC)
[0048] The
composition formulations of the present invention are uniquely
different from other formulations known to the art by a) containing water and
a water
immiscible solvent in a stable, single phase system that forms an emulsion on
dilution
and b) forming stable emulsions upon dilution in an aqueous-based fertilizer,
such as
starter fertilizer 10-34-0. The composition formulations of the present
invention will
likewise form stable emulsions upon dilution with other aqueous-based starter
fertilizers.
[0049] Another use of the surfactant blend shown in TABLE 1 is as a
tank
mix adjuvant. The formula shown in TABLE 1 (2 mL) was mixed with 10-34-0
fertilizer
24
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
(97 mL), and commercial bifenthrin 2 EC (equal to 2 lbs of bifenthrin per
gallon)
formulation (1 mL) in a 100 ml cylinder and repeatedly inverted to insure
complete
mixing and emulsion formation. It was compared to a mixture of 10-34-0 (99 mL)
and
bifenthrin EC (1 mL) prepared in the same manner. The results for the emulsion
stability
of the resulting mixes are shown in TABLE 5. Emulsion stability is evaluated
by the
amount of separation of the oil phase from the fertilizer (aqueous) phase as
seen on the
top of the liquid column.
[0050] TABLE 5 ¨ Summary
Emulsion Stability
Blend Time after mixing (minutes)
1 30 60
10-34-0 plus
Complete separation Complete separatiBifenthrin EC on
Complete separation
10-34-0 plus
Bifenthrin EC plus No separation ¨ No separation ¨ No
separation ¨
surfactant blend of stable emulsion stable emulsion stable
emulsion
Example 1
[0051] The inventive working dilutions of the composition formulations
of
the present invention (in an aqueous-based solution or, preferably, in an
aqueous-based
starter fertilizer), can be used in the methods of the present invention to
treat soil, seeds,
seedlings, and/or crops as treatment targets in need thereof (wherein "crops"
means any
agricultural crop, including but not limited to plants (including but not
limited to grasses,
legumes, fruits, vines, shrubs, trees, etc.) grown for food, feed, seed,
cover, or bio-
material (e.g., fiber, tobacco, etc.), etc.; and wherein "in need thereof'
includes but is not
limited to preventative treatment or treatment of an active pest (e.g., weeds,
insects,
fungus, etc.)). The useful working concentrations of the pesticides identified
above are
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
well known in the art, and a person of skill in the art would readily know how
to reach an
appropriate working concentration of such a pesticide in a composition
formulation of the
present invention for a given application without undue experimentation. The
pesticide
bifenthrin, for example, as formulated above can be added to either water or a
starter
fertilizer solution and 1) added to soil via drip application directly into
the furrow as
crops are planted, 2) shanked into soil before planting, 3) applied via drip
or subterranean
irrigation, 4) applied via overhead irrigation through nozzles onto soil or as
a foliar
application, 5) applied via drench or flood irrigation, or 6) other well-known
and used
methods of application to soil, seeds, seedlings, and/or crops. Additionally,
if a foliar
fertilizer treatment was preferred such as 1) macronutrients N, K, P, S, Ca,
and Mg or 2)
micronutrients Zn, Mn, B, Cl, Cu, Fe, or Mo, or a combination of macro and
micronutrients in their agriculturally acceptable salts, the aqueous EC
formulations could
be simply mixed into the spray water containing the fertilizer elements.
[0052] The
invention has been described with reference to various specific
and preferred embodiments and techniques. However, it should be understood
that many
variations and modifications may be made while remaining within the spirit and
scope of
the invention. It will be apparent to one of ordinary skill in the art that
methods, devices,
device elements, materials, procedures and techniques other than those
specifically
described herein can be applied to the practice of the invention as broadly
disclosed
herein without resort to undue experimentation. All art-known functional
equivalents of
methods, devices, device elements, materials, procedures and techniques
described herein
are intended to be encompassed by this invention. Whenever a range is
disclosed, all
subranges and individual values are intended to be encompassed. This invention
is not to
26
CA 02974506 2017-07-20
WO 2016/118699
PCT/US2016/014234
be limited by the embodiments disclosed, including any shown in the drawings
or
exemplified in the specification, which are given by way of example and not of
limitation.
[0053] While
the invention has been described with respect to a limited
number of embodiments, those skilled in the art, having benefit of this
disclosure, will
appreciate that other embodiments can be devised which do not depart from the
scope of
the invention as disclosed herein. Accordingly, the scope of the invention
should be
limited only by the attached claims.
[0054] All
references throughout this application, for example patent
documents including issued or granted patents or equivalents, patent
application
publications, and non-patent literature documents or other source material,
are hereby
incorporated by reference herein in their entireties, as though individually
incorporated
by reference, to the extent each reference is at least partially not
inconsistent with the
disclosure in the present application (for example, a reference that is
partially inconsistent
is incorporated by reference except for the partially inconsistent portion of
the reference).
27
