U.S. patent application number 15/680331 was filed with the patent office on 2017-12-14 for pesticidal compositions.
This patent application is currently assigned to Syngenta Participations AG. The applicant listed for this patent is Syngenta Participations AG. Invention is credited to Roy Boykin, Jorge Cisneros, Sarah Beth Herzog, Michael James Hopkinson, Jason Keiper, Josh Koon, Jennifer Peterson, Johnny D. Reynolds.
Application Number | 20170354142 15/680331 |
Document ID | / |
Family ID | 41319103 |
Filed Date | 2017-12-14 |
United States Patent
Application |
20170354142 |
Kind Code |
A1 |
Keiper; Jason ; et
al. |
December 14, 2017 |
PESTICIDAL COMPOSITIONS
Abstract
A formulated composition suitable for controlling or preventing
pathogenic damage in a plant comprising (A) at least one solid
active ingredient having a water solubility of at most 100
.mu.g/litre at 25.degree. C. at neutral pH, in an amount of at
least 1 weight %, based on the total weight of the formulated
composition, (B) at least one non-ionic surface active compound
having a hydrophile-lipophile balance (HLB) of between 10 and 18,
one or more customary formulation auxiliaries, and water; wherein
active ingredient (A) is suspended or dispersed in the water, the
weight ratio of surface active compound (B) to active ingredient
(A) is in the range of from 1.5 to 15.0, provided the minimum
amount of surface active compound (B) is at least 6 weight %, based
on the total weight of the formulated composition. Also a method of
improving pesticide residue levels in agriculture.
Inventors: |
Keiper; Jason; (Greensboro,
NC) ; Koon; Josh; (Greensboro, NC) ; Herzog;
Sarah Beth; (Jamestown, NC) ; Hopkinson; Michael
James; (Greensboro, NC) ; Reynolds; Johnny D.;
(Greensboro, NC) ; Peterson; Jennifer; (Tucson,
AZ) ; Boykin; Roy; (Greensboro, NC) ;
Cisneros; Jorge; (Vero Beach, FL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Syngenta Participations AG |
Basel |
|
CH |
|
|
Assignee: |
Syngenta Participations AG
Basel
CH
|
Family ID: |
41319103 |
Appl. No.: |
15/680331 |
Filed: |
August 18, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12993758 |
Apr 18, 2011 |
9770021 |
|
|
PCT/EP2009/056294 |
May 25, 2009 |
|
|
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15680331 |
|
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61052358 |
May 12, 2008 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 25/30 20130101;
A01N 43/90 20130101; A01N 25/30 20130101; A01N 25/04 20130101; A01N
51/00 20130101; A01N 43/90 20130101; A01N 51/00 20130101; A01N
53/00 20130101; A01N 43/56 20130101; A01N 43/56 20130101; A01N
25/04 20130101; A01N 53/00 20130101; A01N 47/34 20130101; A01N
2300/00 20130101; A01N 47/34 20130101; A01N 43/56 20130101; A01N
51/00 20130101; A01N 57/12 20130101; A01N 43/90 20130101; A01N
57/12 20130101; A01N 43/90 20130101; A01N 37/38 20130101; A01N
37/38 20130101; A01N 43/90 20130101; A01N 25/04 20130101 |
International
Class: |
A01N 25/30 20060101
A01N025/30; A01N 51/00 20060101 A01N051/00; A01N 43/56 20060101
A01N043/56; A01N 25/04 20060101 A01N025/04; A01N 37/38 20060101
A01N037/38; A01N 57/12 20060101 A01N057/12; A01N 43/90 20060101
A01N043/90; A01N 47/34 20060101 A01N047/34; A01N 53/00 20060101
A01N053/00 |
Claims
1. An aqueous agrochemical pesticide formulated suspension
concentrate composition comprising: (A) at least one solid active
ingredient having a water solubility of at most 100 .mu.g/litre at
25.degree. C. at neutral pH, wherein the amount of (A) is in the
range of 1.5 to 15 weight % based on the total weight of the
formulated composition; (B) non-ionic surface-active compound
having a hydrophile-lipophile balance (HLB) of between 10 to 18
selected from a polyoxyalkylene-sorbitan ester, castor oil
alkoxylate, alcohol alkoxylate, fatty acid ethoxylate, fatty
monoethanolamide based ethoxylate and block polymers of ethylene
oxide and propylene oxide block, wherein the amount of (B) is in
the range of 6.5 to 25 weight % based on the total weight of the
formulated composition; one or more customary formulation
auxiliaries; and water; wherein the weight ratio of surface-active
compound (B) and active ingredient (A) is in the range of from 1.5
to 15.0; and wherein the suspended particles of active ingredient
(A) have a size from 0.1 to 0.9 .mu.m at x.sub.50 as defined in ISO
13320-1 and a size from 0.7 to 1.5 .mu.m at x.sub.95 as defined in
ISO 13320-1.
2. The composition according to claim 1, wherein the non-ionic
surface-active compound is selected from a sorbitan ester
ethoxylate, castor oil ethoxylate, fatty acid ethoxylate and fatty
alcohol ethoxylate.
3. The composition according to claim 2, wherein the sorbitan ester
ethoxylate is an ethoxylated sorbitan oleate having 20 ethylene
oxide units and having a HLB between 11 and 17.
4. The composition according to claim 2, wherein the castor oil
ethoxylate has 30 to 45 EO groups, such as 30 to 35 ethylene oxide
units and having a HLB of between 10 and 14.
5. The composition according to claim 2, wherein the fatty acid
ethoxylate is an oleic acid having 10 to 30 ethylene oxide units
and having a HLB of between 11 and 15.
6. The composition according to claim 2, wherein the fatty alcohol
ethoxylate is a saturated or unsaturated aliphatic alcohol having 8
to 24 carbon atoms in the alkyl radical, which is derived from the
corresponding fatty acids or from petrochemical products, and
having 1 to 100 ethylene oxide units (EO) and a HLB of between 10
and 13.
7. The composition according to any one of claims 1 to 6, wherein
the active ingredient (A) is selected from abamectin, acrinathrin,
alpha- cypermethrin, acequinocyl, amitraz, benomyl,
beta-cyfluthrin, bifenthrin, bioresmethrin, bistrifluron,
bromopropylate, chlorethoxyfos, chlorfluazuron, clofentezine,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, dodemorph,
esfenvalerate, etofenprox, fenvalerate, flucycloxuron,
flufenoxuron, hydramethylnon, lambda-cyhalothrin, lufenuron,
mecarbam, novaluron, permethrin, phenothrin, silafluofen,
tau-fluvalinate, ZXI 8901 (3-(4- bromophenoxy)-a-cyanobenzyl
2-[4-(difluoromethoxy)phenyl]-3-methylbutanoate) and flubendiamide
(3-iodo-N-(2-mesyl-1,1-dimethylethyl)-N-{4-[1,2,2,2-tetrafluoro-1-(triflu-
oromethyl)ethyl]-o-tolyl}phthalamide), or a mixture thereof.
8. The composition according to claim 1, wherein the active
ingredient (A) is abamectin.
9. The composition according to claim 1, wherein the ratio of
surface active compound (B) to the active ingredient (A) is in the
range of from 1.6 to 10.0.
10. The composition according to claim 1, wherein the ratio of
surface active compound (B) to the active ingredient (A) is in the
range of from 1.7 to 7.0.
11. The composition according to claim 1, wherein the amount of
active ingredient (A) is in the range of 6 to 10, weight percent
and the ratio of (B) to (A) is in the range from 1.5 to 3.0.
12. The composition according to claim 1, wherein the amount of
active ingredient (A) is in the range of 2 to 5, weight percent and
the ratio of (B) to (A) is in the range from 4.0 to 8.0.
13. A method of controlling pathogenic damage or pest damage in a
plant propagation material, a plant, parts of a plant and/or plant
organs that grow at a later point in time, which comprises applying
on the plant, part of the plant, plant organs, plant propagation
material or a surrounding area thereof a composition derived from a
composition according to claim 1.
Description
[0001] This application is a continuation application of U.S. Ser.
No. 12/993,758 filed Nov. 19, 2010, which is a 371 of International
PCT/EP2009/056294 filed May 25, 2009, which claims priority to U.S.
Ser. No. 61/052358 filed May 12, 2008, the contents of which are
incorporated herein by reference.
[0002] The present invention relates to a formulated composition
comprising a certain active ingredient either suspended or
dispersed in water and a defined amount of a defined surface active
compound, a tank-mix composition thereof, and their use for
combating pests. The present invention also relates to a
composition demonstrating improved pesticide residue levels.
[0003] The efficient use of pesticides is often restricted somewhat
by their inherent poor water-solubility. Generally, these
water-insoluble pesticides can be applied to a site in three ways:
1) as a dust, 2) as a solution in an organic solvent or a
combination of water and one or more organic solvents, or 3) as an
emulsion that is prepared by dissolving the product in an organic
solvent, then dispersing the solution in water. All of these
approaches have drawbacks: [0004] application of a dust poses a
health hazard and is inefficient. [0005] solutions and emulsions
requiring an organic solvent as the main carrier are undesirable
since the solvent usually serves no other purpose but to act as a
carrier for the product and as such, the solvent adds an
unnecessary cost to the formulation, and the solvent itself can be
environmentally harmful.
[0006] Another drawback is the efficacy/stability issues associated
with a water-based formulations, such as suspension concentrates
and suspo emulsions. On such example of a drawback is that
water-based formulations containing solid active ingredients or
formulation aids may exhibit settling of the suspended or dispersed
components over time. This settling can lead to the creation of
hard packed sediment making it difficult to get the materials out
of the container. In many cases, the pesticide solids pesticides
may stay suspended in the formulated concentrate but upon dilution
of these types of formulations, the suspended or dispersed solids
will settle with time to the bottom of a container. The rate of
sedimentation depends on a number of factors such as particle size,
particle concentration, viscosity of the suspending medium and the
specific gravity difference between the particles and the
suspending medium. Once settled, the sediments may become hard
packed in nature, making redispersion or resuspension extremely
difficult. The creation of hard packed sediment can occur when the
tanks are not agitated. Interruptions in the spray schedule
frequently occur due to normal breaks, for example overnight, taken
by the applicator, weather changes, mechanical malfunction or
unforeseen events which result in non-agitation of the spray
tank.
[0007] It would be an advantage in the art, therefore, to provide a
pesticide formulation that eliminates the need for organic solvents
as a carrier, on the one hand, but exhibits optimal availability to
the site to which it is applied.
[0008] The efficacy of the active components can often be improved
by addition of other ingredients such as adjuvants. An adjuvant is
defined here as a substance which can increase the biological
activity of an active ingredient but is not itself significantly
biologically active.
[0009] Generally, an adjuvant is added to the spray tank together
with the formulation containing the active ingredient. Further, in
view of an easy and safe handling and dosing of these adjuvants by
the end-user and in view of avoiding unnecessary packing material,
it is desirable to develop concentrated formulations which already
contain such adjuvants.
[0010] However, arriving at a formulation demonstrating
physicochemical stability and biological efficacy is a challenge to
a skilled person.
[0011] The present inventors have found that certain surface active
compounds, when used in a defined amount and a defined ratio with a
low water soluble active ingredient in a formulation offers
benefits hereto before not met with water-based formulations.
[0012] Accordingly, in a first aspect the present invention
provides a formulated composition, preferably an agrochemical
formulated composition, comprising (A) at least one solid active
ingredient having a water solubility of at most 100 .mu.g/litre at
25.degree. C. at neutral pH, in an amount of at least 1 weight %,
based on the total weight of the formulated composition, (B) at
least one non-ionic surface active compound having a
hydrophile-lipophile balance (HLB) of between 10 and 18, one or
more customary formulation auxiliaries, and water
[0013] wherein active ingredient (A) is suspended or dispersed in
the water, the weight ratio of surface active compound (B) to
active ingredient (A) is in the range of from 1.5 to 15.0, provided
the minimum amount of surface active compound (B) is at least 6
weight %, based on the total weight of the formulated
composition.
[0014] The formulated composition of the first aspect demonstrates
improved translaminarity and re-suspension characteristics compared
to a similarly formulated composition which does not comprise said
surface-active compound defined in the first aspect.
[0015] Therefore, in a second aspect the present invention provides
a method of improving the translaminarity of an active ingredient
(A),as defined the first aspect, comprising forming a formulated
composition comprising at least one non-ionic surface active
compound having a hydrophile-lipophile balance (HLB) of between 10
and 18 (compound (B)), wherein the weight ratio of surface active
compound (B) to active ingredient (A) is in the range of from 1.5
to 15.0, provided the minimum amount of surface active compound (B)
is at least 6 weight %, based on the total weight of the formulated
composition.
[0016] In a third aspect, the present invention provides a method
for improving the re-suspension properties of a suspension
comprising forming a composition comprising at least one solid
active ingredient (A), as defined in the first aspect, and at least
one non-ionic surface active compound having a hydrophile-lipophile
balance (HLB) of between 10 and 18 (compound (B)), wherein the
weight ratio of surface active compound (B) to active ingredient
(A) is in the range of from 1.5 to 15.0, provided the minimum
amount of surface active compound (B) is at least 6 weight %, based
on the total weight of the composition.
[0017] The formulated compositions of the present invention at
effective amounts can be not phytotoxic, show rainfastness and
demonstrate improved UV stability, and thereby exhibit optimal
availability to the site to which it is applied. Indeed, it has
been found that the formulated composition of the first aspect
offers acceptable physical, chemical and biological
characteristics.
[0018] Accordingly, in a fourth aspect, the present invention
provides a method of controlling or preventing pathogenic damage or
pest damage in a plant propagation material, a plant, parts of a
plant and/or plant organs that grow at a later point in time, which
comprises applying on the plant, part of the plant, plant organs,
plant propagation material or a surrounding area thereof a
composition derived from the formulated composition defined in the
first aspect.
[0019] A pesticide is a substance or mixture of substances used to
kill a pest. A pesticide may be a chemical substance (such as an
active ingredient), biological agent (such as a virus or bacteria),
antimicrobial, disinfectant or device used against any pest. Pests
include insects, plant pathogens, weeds, molluscs, birds, mammals,
fish, nematodes (roundworms) and microbes that compete with humans
for food, destroy property, spread or are a vector for disease or
cause a nuisance. Although there are benefits to the use of
pesticides, there are also drawbacks, such as potential toxicity to
humans and other animals. Therefore, pesticide residue refers to
the pesticides that may remain on or in food after they are applied
to food crops. An authority in a country, such as the Environmental
Protection Agency (EPA) in USA, sets limits on how much of a
pesticide residue can remain on food and feed products, or
commodities. These pesticide residue limits are known as tolerances
(they are referred to as maximum residue limits, or MRLs, in many
other countries). Tolerances are set to protect consumers from
harmful levels of pesticides on food. Accordingly, EPA is
responsible for regulating the pesticides that are used by growers
to protect crops and for setting pesticide residue in USA.
[0020] Active ingredients mentioned herein are deemed pesticides,
such as active ingredient (A) and active ingredient (D).
[0021] It has been found that use of one or more adjuvants with an
aqueous formulated composition comprising a pesticide, especially
abamectin, reduces the pesticide residue levels on a plant. The
adjuvants referred to herein are those commonly used in the
agriculture, of which a skilled person would know. However, the
present invention especially concerns adjuvants having non-ionic
surfactants and/or oil components, and are commonly known as
non-ionic adjuvants. An adjuvant generally tends to be a mixture or
blend of components.
[0022] Accordingly, in a further aspect the invention provides a
method of improving (or decreasing) the pesticide residue on a
plant comprising applying a tank-mix composition comprising (I) a
pesticidal composition which comprises a pesticide defined in the
first aspect, such as abamectin, a solvent, such as water, and (II)
one or more adjuvants, to the plant, part of the plant, plant
organs, plant propagation material, wherein the adjuvant is present
in an amount of from 0.05 to 0.5% by volume, based on the volume of
the tank-mix composition, and the adjuvant has one or more
non-ionic surfactants and/or oil components.
[0023] In an embodiment, the amount of adjuvant is 0.06 to 0.3,
preferably 0.075 to 0.25, such as 0.08 to 0.15, % by volume based
on volume of the tank-mix composition.
[0024] In an embodiment, the tank-mix composition further comprises
(III) one or more other pesticide formulated compositions
[0025] The adjuvants tend to contain a mixture or blend of
components, such as alcohols, oil components and/or non-ionic
surfactants, including emulsifiers, with the oil components and/or
non-ionic surfactants forming a major proportion of the
adjuvant.
[0026] Examples of oil components in an adjuvant include paraffin
oil, horticultural spray oils (e.g., summer oil), methylated rape
seed oil, highly refined vegetable oil, etc.
[0027] Examples of non-ionic surfactants include polyol fatty acid
esters, polyethoxylated esters thereof, ethoxylated alcohols, alkyl
polysaccharides & blends, amine ethoxylates, sorbitan fatty
acid ester ethoxylates, PEG esters, organosilicone based
surfactants, ethylene vinyl acetate terpolymers, and ethoxylated
alkyl aryl phosphate esters.
[0028] In an embodiment, it has been found that one or more
adjuvants decrease the UV stability of a pesticide, especially
abamectin, i.e, the UV degradation of the pesticide is improved.
Further, the reduced particle size of the pesticide also
contributes to the degradation.
[0029] The invention is described in more detail below.
[0030] Examples of formulation types include [0031] granules [0032]
wettable powders [0033] water dispersable granules (powders) [0034]
water soluble granules [0035] soluble concentrates [0036]
emulsifiable concentrate [0037] emulsions, oil in water [0038]
micro-emulsion [0039] aqueous suspension concentrate [0040] aqueous
capsule suspension [0041] oil-based suspension concentrate, and
[0042] aqueous suspo-emulsion.
[0043] A formulation is referred to as a concentrate when the
concentration of the active ingredient is such that dilution of the
formulation (e.g. with water, solvent) is required before it use
(for example, on a plant, seed or locus thereof). Generally, the
end user will dilute the concentrate to arrive at a spray tank
composition (or mixture) or a tank-mix before using it. Other
formulated pesticidal ingredients and other adjuvants may be
included in the spray tank-composition. Alternatively, depending on
the concentration of the active ingredient in the formulation and
use of the formulation, the end-user could use the formulation
directly, if necessary in combination with other formulation(s),
preferably other pesticidal formulation(s). It would, therefore, be
clear to a skilled person that a formulated composition as defined
in the first aspect corresponds to a formulation, whether as a
concentrate for dilution before use or use without dilution. In an
embodiment, the present invention relates to a concentrated
formulation.
[0044] The present invention is directed to water-based
formulations. In particular, formulations where the solid active
ingredient defined in the first aspect is either suspended or
dispersed in water. Examples of such formulations include
suspension concentrates and suspoemulsions. The active ingredient
can be of any type, or a mixture of different types, preferably at
least one active ingredient in the formulation exhibits nematicide
and/or insecticide efficacy. The formulated composition may
therefore contain organic solvents (such as anti-freeze, etc,) but
not to affect the active ingredient (A)'s suspension or dispersion
in water. Accordingly, a typical volatile organic content (VOC)
level for a formulated composition according to the first aspect is
less than 30, preferably less than 20, especially in the range of 5
to 15, %.
[0045] In the instance the formulated composition comprises one or
more further active ingredient (D) in combination with active
ingredient (A), the or each active ingredient (A) is suspended or
dispersed in an aqueous phase and the or each active ingredient
(D), independently of each other, may be also or dispersed in the
aqueous phase or be provided in an encapsulated form (e.g. as a
microcapsule).
[0046] Solid active ingredients include those solid components that
remain dispersed or suspended in the formulation, including the
diluted composition. Although the pesticidally active ingredients
may exhibit some solubility in the carrier, preferably water,
typically the pesticidally active ingredients will be substantially
insoluble in the selected carrier, such as water. These
substantially water insoluble pesticidally active ingredients may
sometimes be referred to herein for brevity as a "water-insoluble"
active ingredients even if they have measurable solubility in the
selected carrier. It will be apparent to one skilled in the art
that the solubility in water of some active ingredients depends on
pH if they have a titratable acid or base functionality;
specifically acids are more soluble above their pKa and bases are
more soluble below their pKb. Thus acids may be rendered insoluble
in water for the purposes of the present discussion if the aqueous
phase is maintained at a pH close to or below their pKa, even if
they may be more soluble than about 5000 mg/l at a higher pH.
[0047] Specific examples of the active ingredient (A) include
abamectin, acrinathrin, alpha-cypermethrin, acequinocyl, amitraz,
benomyl, beta-cyfluthrin, bifenthrin, bioresmethrin, bistrifluron,
bromopropylate, chlorethoxyfos, chlorfluazuron, clofentezine,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, dodemorph,
esfenvalerate, etofenprox, fenvalerate, flucycloxuron,
flufenoxuron, hydramethylnon, lambda-cyhalothrin, lufenuron,
mecarbam, novaluron, permethrin, phenothrin, silafluofen,
tau-fluvalinate, ZXI 8901 (3-(4-bromophenoxy)-a-cyanobenzyl
2-[4-(difluoromethoxy)phenyl]-3-methylbutanoate), and flubendiamide
(3-iodo-N-(2-mesyl-1,1-dimethylethyl)-N-{4-[1,2,2,2-tetrafluoro-1-(triflu-
oromethyl)ethyl]-tolyl}phthalamide).
[0048] In an embodiment of each aspect of the present invention, at
least one active ingredient (A) is selected from abamectin, and
lufenuron; preferably active ingredient (A) is abamectin.
[0049] Surfactants generally tend to have a HLB of between 4 to 27
and are of different types. It is has been found that non-ionic
surface active compounds with a defined HLB have advantageous
properties when used in defined amounts and ratios with specific
active ingredients, preferably if the active ingredients have a
particular particle size.
[0050] The compound (B) is preferably a non-ionic surface-active
compound or mixture of compounds having a hydrophile-lipophile
balance (HLB) of between 10 to 18. Examples of non-ionic
surface-active compounds (compound B) particularly suitable for the
present invention include a polyoxyalkylene-sorbitan ester, castor
oil alkoxylate, alcohol alkoxylate, fatty acid ethoxylate, fatty
monoethanolamide based ethoxylate and block polymers of ethylene
oxide and propylene oxide block.
[0051] In an embodiment, the polyoxyalkylene-sorbitan ester is
ethoxylated, propoxylated, butoxylated and mixed ethoxy/propoxy
and/or ethoxy/butoxy analogues having a C8-22 alkyl or alkenyl
group and up to 20 ethlyleneoxy and/or propyleneoxy and/or
butyleneoxy groups. A preferred polyoxyalkylene-sorbitan ester is
ethoxylated sorbitan mono-ester (such as oleate or laurate),
especially having on average 20 ethyleneoxy groups, which are
ATPLUS 309 F (UNIQEMA), the ALKAMULS series (RHODIA) or TWEEN
series (such as TWEEN 80, TWEEN 20, TWEEN 21) (CRODA-UNIQEMA). In a
preferred embodiment, the polyoxyalkylene-sorbitan ester has a HLB
between 11 and 17 such as between 12 and 17, especially 14 to 17,
and preferably the saponification number being 45 to 55.
[0052] In an embodiment, the alcohol alkoxylate has an average
molecular weight of less than 10000, more preferably less than
7000, especially less than 5000, such as in the range of 200 to
3500. Suitable examples are preferably polyethoxylated, saturated
and unsaturated aliphatic alcohols, having 8 to 24 carbon atoms in
the alkyl radical, which is derived from the corresponding fatty
acids or from petrochemical products, and having 1 to 100,
preferably 2 to 50, ethylene oxide units (EO), it being possible
for the free hydroxyl group to be alkoxylated, which are
commercially available, for example as GENAPOL X, GENAPOL OA,
GENAPOL OX, GENAPOL UD, GENAPOL LA and GENAPOL O series (CLARIANT),
CROVOL M series (CRODA) or as LUTENSOL series (BASF), or are
obtainable therefrom by etherification, for example GENAPOL X080. A
preferred surface active compound is an oleylpolyglycol ether, such
as with 8 to 20 ethylene oxide units (for example, GENAPOL 0100,
SYNPERONIC A20) and a tridecyl alcohol ethoxylate. In a preferred
embodiment, the polyalkoxylated alcohol alkoxylate has a HLB of
between 10 and 13, preferably from 10.5 and 12.
[0053] In an embodiment, the castor oil alkoxylate is castor oil
ethoxylate having preferably 30 to 45 EO groups, such as 30 to 35
EO groups. Examples include the AQNIQUE CSO series (COGNIS),
TOXIMUL series(such as TOXIMUL 8240) (STEPAN) and ALKAMULS EL
series (RHODIA). In a preferred embodiment, the HLB of the castor
oil alkoxylate is between 10 and 14, such as between 11 and 13, and
preferably the saponification number being 65 to 75, such as 67 to
71, mg KOH/g.
[0054] In an embodiment, the fatty acid ethoxylate is an
ethoxylated fatty acid, such as oleic acid, having 10 to 30 EO
groups, preferably 10 to 20 EO groups. Examples include NINEX
series (such as NINEX MT-615) (STEPAN) and AGNIQUE FAC series
(COGNIS). In a preferred embodiment, the HLB of the fatty acid
ethoxylate is between 11 and 15, such as between 12 and 14.
[0055] In an embodiment, the fatty monoethanolamide based
ethoxylate has C12 to C22 saturated or unsaturated acid alkyl chain
with 10 to 40 EO groups. Examples include the NINOL series (STEPAN)
and the AGNIQUE AAM (COGNIS) series. Preferably the HLB is 10 to
18, such as between 11 and 15, such as between 12 and 14.
[0056] In an embodiment, block polymers of ethylene oxide and
propylene oxide block can be di- and tri-block copolymers, such as
ABA or BAB block copolymer or BA block copolymers. Examples include
the GENAPOL PF series (CLARIANT), the PLURONIC series (BASF), the
SYNPERONIC PE series (UNIQEMA), or the TOXIMUL series (STEPAN). A
preferred group of ethylene oxide/propylene oxide block copolymers
for use in the compositions of this invention are butyl based
poly(oxypropylene) poly(oxyethylene) block copolymers having an
average molecular weight in a range of 2,400 to 3,500 (e.g. TOXIMUL
8320, Stepan Chemical Co.). Suitable examples include Pluronic L10,
Pluronic L44 , Pluronic L63, Pluronic L64, Pluronic P84, Pluronic
P104, Pluronic P105, Step-Flow 26, Toximul 8323, and Toximul 8320.
Preferably the HLB is 10 to 18, such as 11 to 16.
[0057] Preferred surface active compounds (B) are sorbitan ester
ethoxylates, castor oil ethoxylates, fatty acid ethoxylates and
fatty alcohol ethoxylates.
[0058] In an embodiment, [0059] the sorbitan ester ethoxylate is an
ethoxylated sorbitan oleate having 20 ethyleneoxy groups and having
a HLB between 11 and 17 such as between 12 and 17, especially 14 to
17; [0060] the castor oil ethoxylate has 30 to 45 EO groups, such
as 30 to 35 EO groups and having a HLB of between 10 and 14, such
as between 11 and 13; [0061] the fatty acid ethoxylate is a oleic
acid having 10 to 30 EO groups, preferably 10 to 20 EO groups and
having a HLB of between 11 and 15, such as between 12 and 14; and
[0062] the fatty alcohol ethoxylate is a saturated or unsaturated
aliphatic alcohol having 8 to 24 carbon atoms in the alkyl radical,
which is derived from the corresponding fatty acids or from
petrochemical products, and having 1 to 100, preferably 2 to 50,
ethylene oxide units (EO) and having a HLB of between 10 and 13,
preferably from 10.5 and 12.
[0063] In an embodiment, the amount of surface active compound (B)
in a formulation is at least 6.5 to 25, preferably 7 to 20,
preferably in the range of from 7 to 18, weight %, based on the
total weight of the formulated composition.
[0064] In an embodiment, the ratio of surface active compound (B)
to the active ingredient (A) is in the range of from 1.6 to 10.0,
preferably 1.7 to 7.0.
[0065] In an embodiment, the amount of active ingredient (A),
especially abamectin, is in the range of from 1.5 to 15, preferably
1.5 to 10, especially 2 to 9, weight %, based on the total weight
of the formulated composition.
[0066] In an embodiment, the amount of active ingredient (A) is in
the range of 6 to 10, preferably 7 to 9, weight % and the ratio of
(B) to (A) is in the range of from 1.5 to 3.0, preferably 1.7 to
2.5. In such an instance, the active ingredient is preferably
abamectin and surface active compound is preferably a sorbitan
ester ethoxylate.
[0067] In an embodiment, the amount of active ingredient (A) is in
the range of 2 to 5, preferably 2.5 to 4.5, weight % and the ratio
of (B) to (A) is in the range of from 4.0 to 8.0, preferably 5.0 to
6.5. In such an instance, the active ingredient is preferably
abamectin and surface active compound is preferably a sorbitan
ester ethoxylate and optionally a second active ingredient (D) is
also present.
[0068] In an embodiment, the amount of active ingredient (A) is in
the range of 2 to 5, preferably 2.5 to 4.5, weight % and the ratio
of (B) to (A) is in the range of from 4.0 to 7.0, preferably 4.5 to
5.5. In such an instance, the active ingredient is preferably
abamectin and surface active compound is preferably a sorbitan
ester ethoxylate and optionally a second active ingredient (D) is
also present.
[0069] In an embodiment, the amount of active ingredient (A) is in
the range of 1.0 to 3.0, preferably 1.5 to 2.5, weight % and the
ratio of (B) to (A) is in the range of from 2.5 to 7.0, preferably
4.0 to 5.5. In such an instance, the active ingredient is
preferably abamectin and surface active compound is preferably a
sorbitan ester ethoxylate and optionally a second active ingredient
(D) is also present.
[0070] In an embodiment, the amount of active ingredient (A) is in
the range of 1.0 to 3.5, preferably 1.5 to 3.0, weight % and the
ratio of (B) to (A) is in the range of from 2.0 to 6.0, preferably
3.0 to 5.0. In such an instance, the active ingredient is
preferably abamectin and surface active compound is preferably a
sorbitan ester ethoxylate and optionally a second active ingredient
(D) is also present.
[0071] The correct choice of suitable formulation auxiliary
components for the formulation often determines to a significant
extent whether the active ingredient can display its full efficacy
after application. When selecting suitable ingredients to ensure
the physicochemical stability of the formulation, it must be taken
into account that not every active ingredient can be processed into
any given formulation type without losses in stability and/or
efficacy. The appropriate choice and amount of other the customary
formulation auxiliaries, such as surfactants, wetting agents,
anti-foam, anti-freeze, thickener, pH buffer, preservative, etc is
known to a skilled person realising that a formulated composition
comprising (A) and (B), and optionally one or more further active
ingredients, is to be formulated in a water-based composition.
[0072] In an embodiment, it has been found that the formulation
defined in the first aspect benefits also from presence one or more
other surface compounds different to (B), designated hereinafter as
surface compound (C). In a preferred embodiment, surface compounds
(C) are alkoxylated polyarylphenols and alkoxylated polyarylphenol
phosphates.
[0073] In an embodiment, the alkoxylated polyarylphenol is a
polyethoxylated, arylalkylphenols, such as, for example,
2,4,6-tris(1-phenylethyl)phenol (tristyrylphenol) having an average
degree of ethoxylation of between 10 and 80, preferably from 16 to
40, such as SOPROPHOR BSU (RHODIA). Also suitable are EO/PO block
copolymers of polyarylphenols, such as SOPROPHOR 796/P (RHODIA) and
STEP-FLOW 1500 (STEPAN).
[0074] Examples of a phosphate type surfactant include an
alkylphenol polyalkoxyether phosphate, a block copolymer of
polyalkoxyether phosphate, a polyarylphenol polyalkoxyether
phosphate and an arylphenol polyalkoxyether phosphate, such as
SOPROPHOR 3D33 (RHODIA).
[0075] In a preferred embodiment, the formulated composition of the
first aspect further comprises, as a surface active compound (C),
an ethoxylated tristyrylphenol and/or an ethoxylated
tristyrylphenol phosphate.
[0076] In an embodiment, each surface active (C) is present in an
amount of at most 3, preferably 2.8, such as 0.5 to 2.5, weight %,
based on the total weight of the formulation.
[0077] In the instance there are two or more surface active
compounds (C) present, the ratio of any two, preferably non-ionic
(C) to ionic (C), is in the range of 1:3 to 3:1, such as 2:5 to
4:2, preferably 1:2. to 3:2. Preferably the ionic surface active
compound (C) is anionic, such as an ethoxylated (tristyrylphenol
phosphate) and the non-ionic surface active compound (C) is an
ethoxylated 2,4,6-tris(1-phenylethyl)phenol (tristyrylphenol).
[0078] In an embodiment, the formulation of the first aspect also
benefits from one or more oil inerts, such as medium chain
triglycerides (such as STEPAN 108) and rape seed oil methyl ester
(such as STEPOSOL ROE-W).
[0079] The formulation of the present invention may further
comprise other formulation auxiliaries known in the art of
agrochemical formulations in customary amounts. Such auxiliaries
include, but are not limited to, surfactants (such as anionic,
non-ionic, cationic), antifreeze agents (such as but not limited to
glycerine, ethylene glycol, propylene glycol, monopropylene glycol,
hexylene glycol, 1-methoxy-2-propanol, cyclohexanol), buffering
agents (such as but not limited to sodium hydroxide, phosphoric
acid), preserving agents (such as but not limited to derivatives of
1,2-benzisothiazolin-3-one, benzoic acid, sorbic acid,
formaldehyde, a combination of methyl parahydroxybenzoate and
propyl parahydroxybenzoate), stabilizing agents (such as but not
limited to acids, preferably organic acids, such as dodecylbenzene
sulfonic acid, acetic acid, propionic acid or butyl hydroxyl
toluene, butyl hydroxyl anisole), thickening agents (such as but
not limited to heteropolysaccharide and starches), and antifoaming
agents (such as but not limited to those based on silicone,
particularly polydimethylsiloxane). Such auxiliaries are
commercially available and known in the art.
[0080] In an embodiment, the formulation according to the first
aspect further comprises one or more other active ingredients (D)
different from (A). The other active ingredient can be of any type
(e.g. herbicide, fungicide, insecticide, nematicide, etc), and can
be of the same type as the active ingredient (A).
[0081] Examples of suitable other active ingredient include
thiamethoxam, imidacloprid, clothianidin, tefluthrin, cyflumetofen,
chlorantraniliprole, cyantraniliprole, difenconazole, fipronil,
azoxystrobin and fludioxonil.
[0082] In an instance, the formulated composition comprises
abamectin, and one or more selected from thiamethoxam,
imidacloprid, clothianidin, lufenuron, lambda cyhalothrin,
tefluthrin, cyflumetofen, chlorantraniliprole, cyantraniliprole,
difenconazole, fipronil, azoxystrobin and fludioxonil.
[0083] The amount of the other active ingredient (D) can be from 1
to 30, preferably 2 to 20, such as 5 to 15, weight %, based on the
total weight of the formulation.
[0084] In an embodiment, the formulation comprises abamectin and
thiamethoxam.
[0085] In an embodiment, the formulation comprises abamectin and
chlorantraniliprole.
[0086] In an embodiment, the formulation comprises abamectin and
cyantraniliprole.
[0087] In the instance of a mixture of active ingredients, the
ratio of the other active ingredient (D) to active ingredient (A)
can be 1:1 to 8:1, preferably 2:1 to 6:1.
[0088] In an embodiment, the formulation comprises abamectin and
thiamethoxam, wherein ratio of thiamethoxam to abamectin is in the
range of from 3.0 to 5.5, abamectin is present in an amount of
according 2.5 to 4.5 weight %, and the ratio of (B) to (A) is in
the range of 5.0 to 6.5.
[0089] In an embodiment, the formulation comprises abamectin and
chlorantraniliprole, wherein ratio of chlorantraniliprole to
abamectin is in the range of from 2.0 to 3.0, abamectin is present
in an amount of 1.5 to 2.5 weight %, and the ratio of (B) to (A) is
in the range of 4.0 to 5.5.
[0090] In an embodiment, the formulation comprises abamectin and
chlorantraniliprole, wherein ratio of chlorantraniliprole to
abamectin is in the range of from 3.5 to 4.5, abamectin is present
in an amount of 1.5 to 3.0 weight %, and the ratio of (B) to (A) is
in the range of 3.0 to 5.0.
[0091] In an embodiment, the formulation comprises abamectin and
thiamethoxam, wherein the ratio of thiamethoxam to abamectin is in
the range of from 1.5 to 2.5, abamectin is present in an amount of
3 to 9 weight %, and the ratio of (B) to (A) is in the range of 2
to 7, preferably 2.5 to 5.5.
[0092] The process for preparing the formulations of the invention
are customary, and involves grinding the solid particles, such the
active ingredient(s), optionally with formulation auxiliaries, with
a mill to obtain the desired particle size and then combining with
formulation auxiliaries and solvent. In an embodiment, horizontal
bead mill such as a Netzsch zeta mill is advantageous. The mill
media is composed of either glass, ceramic, ceria stabilized
ceramic, or yttria stabilized ceramic beads in the size range of
0.3 mm-1.2 mm. Other types of milling equipment used include Drais
mill, dyno mill, and/or an attritor. The solid particles size are
reduced by passing the formulation through a grinding chamber where
the media is circulated at high speeds in order to fracture the
particles. In the case of a mixture of solid active ingredients,
the active ingredients can be milled together, or separately and
then combined to arrive at the formulation.
[0093] Generally the formulated compositions can be prepared as
follows:
[0094] Technical grade active ingredient (compound A) is added, in
solid form, to an aqueous solution containing at least one
surfactant that suitably wets the solid, allowing for a
concentrated crude suspension (typically 20-60 wt. % active
ingredient). This solution may contain multiple surfactants to aid
in dispersion and lubrication of the particles in the milling
process, as well as components such as antifoam, antifreeze, pH
adjustors and preservative. This suspension is mixed thoroughly
with a suitable mixing device such as a Cowles blade or
rotor-stator mixer before particle size reduction via milling.
[0095] The milling process, depending on the equipment used and the
active ingredient being milled, can be carried out with a single
mill, or alternatively multiple devices where the initial particle
size is reduced with one mill, and ground to finer sizes with
another mill. Appropriate devices for the first step of the
two-step scenario include attritors, colloid mills, Dyno-mills and
Eiger mills where milling media may consist of a variety of
compositions and the media sizes are generally greater than 1 mm
(nominally spherical beads). Appropriate devices for the second
step of the two-step scenario include high-energy mills such as the
Netzsch Lab Mini Zeta and the Drais Superflow. Milling media for
these devices typically have diameters 1 mm or below and can
consist of hard, dense materials such as yttrium.
[0096] Milling of the suspension from crude to fine particle sizes
can be carried out by either recirculating the fluid or subjecting
the fluid to multiple passes through the milling chamber, depending
on the nature of the milling device. As the particle size of the
solids is reduced, heat is generated, requiring cooling of the
suspension.
[0097] Once the desired particle size of this suspension, as
measured by an appropriate light scattering device, is achieved, it
is either ready for subsequent formulation to the composition of
the invention or can be further stabilized through use of a
thickener such as a xanthan gum. This suspension is referred to as
a "millbase".
[0098] The final formulated composition concentrate is formulated
with appropriate components such as water, antifoam, antifreeze,
preservatives, rheology modifiers and suspension aids, additional
surfactants that serve to disperse the solids in concentration and
when applied in dilute form, and in the case of the present
invention, a non-ionic surface active compound defined in the first
aspect (compound B), and optionally with millbases of other active
ingredients. Mixing is typically achieved with standard impellers
that allow for appropriate bulk agitation, and where necessary,
higher shear dispersion. In the instance that a second millbase
composition is of a capsule suspension, a formulator would take
appropriate known precautions (such as the avoidance of high shear)
to ensure capsule integrity. In some instances, a mixture of active
ingredients may be co-milled together (e.g., abamectin and
chlorantraniliprole) form a desired particle size of the suspension
mixture and then this millbase formulated with other formulation
auxiliaries to result in a formulation composition according to the
invention.
[0099] The order of addition of the final formulation components
can vary and depends on a number of factors, including available
equipment and time required to mix certain components.
[0100] In a preferred embodiment, a formulation defined in the
first aspect has suspended particles of active ingredient (A)
having a size of from 0.1 to 0.9, preferably 0.4 to 0.8, especially
0.5 to 0.8, .mu.m, at x.sub.50 as defined in ISO 13320-1.
[0101] In a preferred embodiment, a formulation defined in the
first aspect has suspended particles of active ingredient (A)
having a size of from 0.7 to 1.5, preferably 0.9 to 1.5, especially
1.0 to 1.4, .mu.m, at x.sub.95 as defined in ISO 13320-1
[0102] The particle size of a second or further active ingredient
(D90) may be the same or different from the particle size of the
active ingredient (A). In an embodiment, the particle size of
chlorantraniliprole is from 0.1 to 0.9, preferably 0.1 to 0.8,
especially 0.15 to 0.8, .mu.m, at x.sub.50 as defined in ISO
13320-1.
[0103] In an embodiment, the particle size of chlorantraniliprole
is from 0.1 to 0.9, preferably 0.4 to 0.8, especially 0.5 to 0.8,
.mu.m, at x.sub.50 as defined in ISO 13320-1.
[0104] Further, the particle size of the formulated composition
could differ from the particle size of the desired active
ingredient (A) because the formulated composition has other solid
or dispersed components, such as colorants and other solid active
ingredients (D).
[0105] In an embodiment, the particle size of the formulated
composition is 0.7 to 1.5, preferably 0.9 to 1.5, especially 1.0 to
1.4, .mu.m, at x.sub.95 as defined in ISO 13320-1, and
independently of the x.sub.95 size, a particle size of 0.1 to 0.9,
preferably 0.4 to 0.8, especially 0.5 to 0.8, .mu.m, at x.sub.50 as
defined in ISO 13320-1.
[0106] In an embodiment, the formulation according to the first
aspect is in the form of a suspension concentrate or
suspoemulsion.
[0107] Whereas commercial formulations will be formulated as
concentrates (known as a pre-mix composition (or concentrate,
formulated compound (or product)), the end user (e.g., farmer,
grower or plant propagation material treater) will normally employ
them after dilution with a solvent (such as water), optionally also
containing one or more other pesticide pre-mixes and formulation
auxiliaries. The diluted version of the pesticidal compositions is
known as a tank mix composition (or ready-to-apply, spray broth, or
slurry). The end user of the pesticidal composition can also use
the commercial pesticidal compositions (formulations) without
further dilution in certain circumstances. Accordingly, a
pesticidal composition as used herein refers to a pre-mix
composition or a tank mix composition.
[0108] As with the nature of the formulations, the methods of
application, such as foliar, drench, spraying, atomizing, dusting,
scattering, coating or pouring, are chosen in accordance with the
intended objectives and the prevailing circumstances.
[0109] The tank-mix compositions are generally prepared by diluting
with a solvent (for example, water) the one or more pre-mix
compositions containing different pesticides, and optionally
further auxiliaries.
[0110] Suitable carriers and adjuvants can be solid or liquid and
are the substances ordinarily employed in formulation technology,
e.g. natural or regenerated mineral substances, solvents,
dispersants, wetting agents, tackifiers, thickeners, binders or
fertilizers.
[0111] Generally, a tank-mix formulation for foliar or soil
application comprises 0.1 to 20%, especially 0.1 to 15%, active
ingredient compound(s), and 99.9 to 80%, especially 99.9 to 85%, of
a solid or liquid auxiliaries (including, for example, a solvent
such as water), where the auxiliaries can be a surfactant in an
amount of 0 to 20%, especially 0.1 to 15%, based on the tank-mix
formulation.
[0112] Normally, a tank-mix formulation for seed treatment
application comprises 0.25 to 80%, especially 1 to 75%, active
ingredient compounds, and 99.75 to 20%, especially 99 to 25%, of a
solid or liquid auxiliaries (including, for example, a solvent such
as water), where the auxiliaries can be a surfactant in an amount
of 0 to 40%, especially 0.5 to 30%, based on the tank-mix
formulation.
[0113] The formulated compositions according to the present
invention can therefore also be used in combination with other
pesticidal formulations, formulation auxiliaries, and adjuvants (a
substance which in itself doesn't show pesticidal activity--usually
crop oil concentrates and mixture of surfactants).
[0114] In an embodiment, non-ionic adjuvants are preferred for use
with the pesticidal compositions of the invention.
[0115] Examples of non-ionic adjuvants product ranges include
ATPLUS.TM., ATPLUS.TM. MBA, BRIJ, .TM. SYNPERONIC.TM., ATLAS.TM. G,
ATLOX.TM., TWEEN.TM., and CROVOL.TM.. Specific examples include
PENETRATOR.TM., PENETRATOR Plus.TM., ADIGOR.TM., AGORA.TM.,
ATPLUS.TM. 411 F, ATPLUS.TM. 463, SILWET.TM. L77, ATLOX.TM. SEMKOTE
E-135, ALKAMUL.TM. BR, TURBOCHARGE.TM. D, CET SPEED.TM.,
DYNE-AMIC.TM..
[0116] Specific examples are: [0117] DYNE-AMIC.TM. is a blend of
highly refined vegetables oils combined with an organosilicone
based surfactants. [0118] ATPLUS 411 F is a mixture of paraffin
based petroleum oil and a surfactant blend. [0119] ATPLUS 463 is a
blend of mineral oil and non-ionic surfactants. [0120] PENETRATOR
Plus is a mixture of light to mid range paraffin oil, polyol fatty
acid esters, polyethoxylated esters thereof, ethoxylated alkyl aryl
phosphate esters. [0121] SILWET L-77 is a polyalkyleneoxide
modified heptamethyltrisiloxane. [0122] TURBOCHARGE D is a blend of
mineral oil and non-ionic surfactants. [0123] ALKAMUL BR is a
castor oil ethoxylate 40. [0124] CET SPEED is a blend of oleyl
alcohol poylglycol ethers. [0125] ADIGOR is a blend of petroleum
distillates, methyl ester of of fatty acids and alcohol ethoxylate.
[0126] AGORA is a blend of petroleum oil, alcohol and an emulsifier
blend. [0127] ATLOX SEMKOTE E-135 is an ethylene vinyl acetate
terpolymer.
[0128] Use of certain adjuvants in a tank-mix composition
containing certain pesticides offer unexpected benefits in respect
of pesticide residue level management. Such adjuvants are non-ionic
adjuvants as described herein. The pesticides are those defined in
the first aspect, preferably abamectin.
[0129] The present invention provides a method of controlling or
preventing pathogenic damage or pest damage. The present
formulations and aqueous pesticidal suspension compositions may be
of use for different purposes (such as foliar, soil or plant
propagation material treatment) for the control of pathogenic
and/or pest damage.
[0130] The pathogens and/or pests controlled would depend on the
active ingredient(s) present in the applied composition.
[0131] The amount of active ingredient used for pathogenic and/or
pest control would vary according to the specific active ingredient
(e.g., abamectin is generally applied at a lower rate than
lambda-cyhalothrin, nature of the soil, type of crop plant,
prevailing climatic conditions, and can be determined by biology
trials.
[0132] Typical application rate of abamectin to the locus of the
crop plant is from 1 to 100 g per hectare (g/ha), such as 3 to 90
g/ha, especially from 6 to 60 g/ha, preferably from 9 to 36 g/ha,
most preferably from 12 to 27 g/ha. The pesticide may be applied
once or several occasions during the growth of a plant depending on
the plant and circumstances, for example, 1 to 6 or 1 to 4
occasions (for a tomato crop harvest, for example, the combination
can be applied up to 6 times before harvest), and the amounts
indicated above are for each application.
[0133] The amount of active ingredient used on the propagation
material varies according to specific active ingredient (e.g.,
abamectin is generally applied at a lower rate than
lambda-cyhalothrin, type of propagation material (e.g., seed or
tuber) and plant (for example, wheat seeds generally have less
active ingredients adhered thereto than oil seed rape seeds based
on equivalent weight of seeds) and is such that the defined
pesticide particles is an effective amount to provide the desired
pesticidal action and can be determined by biology trials.
[0134] The application rates can, therefore, range from 6 g to 250
kg of per 100 kg of seeds. Generally, the application rate for
cereal seeds range from 23 g to 740 g, preferably 5 g to 600 g, per
100 kg of seeds; and the application rate for oil seed rape seeds
can range from 700 g to 25 kg, preferably 1.5 kg to 20 kg, per 100
kg of seeds. Generally treatment rate of abamectin on to a cotton
seed is in the range of 0.1 to 0.2 mg ai/seed, to a tomato seed is
in the range of 0.3 to 0.6 mg ai/seed and to a soybean seed is in
the range of 0.1 to 0.2 mg ai/seed.
[0135] Therefore, the present invention also provides a plant
propagation material treated with the formulation and aqueous
suspension composition defined in the first and second aspect
respectively.
[0136] The present invention is especially suitable for
agronomically important plants, which refers to a plant that is
harvested or cultivated on a commercial scale.
[0137] Examples of such agronomic plants (or crops) are cereals,
such as wheat, barley, rye, oats, rice, maize or sorghum; beet,
such as sugar or fodder beet; fruit, for example pome fruit, stone
fruit and soft fruit, such as apples, pears, plums, prunes,
peaches, almonds, cherries or berries, for example strawberries,
raspberries or blackberries; legumes, such as beans, lentils, peas
or soya beans; oil crops such as oil seed rape, mustard, poppies,
olives, sunflowers, coconuts, castor, cacao or peanuts; the marrow
family, such as pumpkins, cucumbers or melons; fibre plants such as
cotton, flax, hemp or jute; citrus fruits such as oranges, lemons,
grapefruits or tangerines; vegetables such as spinach, lettuce,
asparagus, cabbage species, carrots, onions, chillis, tomatoes,
potatoes, or capsicums; the laurel family such as avocado,
Cinnamonium or camphor; and tobacco, nuts (such as walnut), coffee,
egg plants, sugar cane, tea, pepper, grapevines, hops, the banana
family, latex plants and ornamentals. Also important are forage
crops such as grassed and legumes.
[0138] Suitable target crops also include transgenic crop plants of
the foregoing types. 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 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 toxins, have been disclosed, for example, in EP-A-0 374 753,
WO 93/07278, WO 95/34656, EP-A-0 427 529 and EP-A-451 878 and are
incorporated by reference in the present application.
[0139] A description of the structure of the pesticides mentioned
herein can be found in the e-Pesticide Manual, version 3.1, 13th
Edition, Ed. CDC Tomlin, British Crop Protection Council,
2004-05.
[0140] In each aspect and embodiment of the invention, "consisting
essentially" and inflections thereof are a preferred embodiment of
"comprising" and its inflections, and "consisting of" and
inflections thereof are a preferred embodiment of "consisting
essentially of" and its inflections.
[0141] The following Examples are given by way of illustration and
not by way of limitation of the invention.
EXAMPLES
Preparation Examples
[0142] P.1--Preparation of an Abamectin Millbase
[0143] In a suitably-sized vessel, polyarylphenol alkoxylate
(Soprophor BSU, 28.4 g) and polyarylphenol alkoxylate phosphate
(Soprophor 3D33, 18.9 g) were added to potable water (622.5 g) and
mixed. Propylene glycol (94.7 g), antifoam (Antifoam 1510, 3.8 g)
were further added with mixing, followed by Abamectin (900 g). The
pH of the mixture was adjusted to approximately pH 6 using sodium
hydroxide (25% in water, 1.2 g). The crude suspension was first
passed through a Dyno-Mill (0.6 liter mill chamber volume) to
reduce particle size of the suspended particles below 50
micrometers, followed by milling in recirculation mode on Netzsch
Lab Mini Zeta IIE mill until the particle size of the suspended
particles was below 1.5 micrometers (X.sub.95).
[0144] P.2--Preparation of Example 2
[0145] In a suitably-sized vessel, propylene glycol (31.3 g),
polyarylphenol alkoxylate (Soprophor BSU, 6.2 g), polyarylphenol
alkoxylate phosphate (Soprophor 3D33, 22.5 g), polyoxalkylene
sorbitan ester (Tween 80, 127.7 g), preservative (Proxel GXL, 0.6
g) and antifoam (Antifoam 1510, 1.3 g) were mixed using a Cowles
impeller. Potable water (442.0 g) and Abamectin millbase (P.1,
120.0 g) were added with continued mixing. Thickener (Kelzan, 1.9
g) was added with mixing for one hour to assure satisfactory
dispersion. The pH of the suspension concentrate was adjusted to
approximately 6 with sodium hydroxide (25% in water, 1.0 g).
P.3--Preparation of Example 13
[0146] Step 1: In a suitably-sized vessel, propylene glycol (119.2
g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 40.6 g)
and polyarylphenol alkoxylate (Soprophor BSU, 20.1 g) were mixed to
homogeneity. Potable water (517.1 g), antifoam (Antifoam 1500, 1.0
g) and potassium hydroxide (50% in water, 1.99 g) were further
added with mixing, followed by an active ingredient (D) (287.4 g).
The crude suspension was milled with a Netzsch Lab Mini Zeta IIE
mill until the particle size of the suspended particles is below
1.2 micrometers (X.sub.95) to yield a millbase of the active
ingredient.
[0147] Step 2: Thereafter, in a suitably-sized vessel, propylene
glycol (485.3 g), polyoxyalkylene sorbitan ester (Tween 80, 400.0
g), polyarylphenol alkoxylate phosphate (Soprophor 3D33, 59.1 g)
and polyarylphenol alkoxylate (Soprophor BSU, 75.1 g) were mixed to
homogeneity. Potable water, antifoam (Antifoam 1500, 13.1 g)
potassium hydroxide (50% in water, 2.6 g), preservative (Proxel
GXL, 12.5 g) were added with mixing followed by Abamectin millbase
(P.1, 171.7 g) and millbase prepared in step 1 (30 wt. %, 750.2 g).
Thickener (Rhodopol 23, 9.5 g) and suspending agent (Attaflow Fla.,
100.1 g) were added and mixed to fully disperse.
P.4--Preparation of Example 15
[0148] Step 1: In a suitably-sized vessel, potable water (3104.0
g), lignosulfonate (Borresperse NA, 61.2 g), propylene glycol
(243.9 g), polyarylphenol alkoxylate phosphate (Soprophor 3D33,
175.5 g) and antifoam (Antifoam 1510, 30.9 g) were mixed with
moderate agitation using a Cowles impeller. Active ingredient (D)
(2442.3 g) was added until well-mixed. The pH of the crude
suspension was adjusted with sodium hydroxide (25% in water, 8.6 g)
to approximately 4.6. The suspension was milled with two passes
through a Dyno-mill (0.6 liter mill chamber), resulting in particle
size of 8.0 micrometers (X.sub.95) to yield a millbase of the
active ingredient.
[0149] Step 2: Thereafter, in a suitably-sized vessel, potable
water (6700.0 g) and polyoxyalkylene sorbitan ester (Tween 80,
1996.0 g) were added with moderate agitation to homogeneity.
Preservative (Proxel GXL, 8.1 g), millbase prepared in step 1
(2042.0 g) and Abamectin millbase (P.1, 819.6 g) and suspending
agent (Attaflow FL, 236.0 g) were added and mixed with moderate
agitation. Thickener (Rhodopol 23, 18.7 g) was slowly added with
high agitation. The pH is adjusted to approximately 6.5 with sodium
hydroxide (25% in water, 0.5 g) and the suspension concentrate was
further mixed for one hour.
P.5--Preparation of Example E
[0150] Step 1: Thereafter, in a suitably-sized vessel,
suspoemulsion (P.6, 62.49 g), potable water (52.73 g), preservative
(Acticide GA, 0.23 g) and antifoam (Antifoam 1500, 0.19 g) were
added with moderate agitation to homogeneity. Abamectin millbase
(P.1, 4.33 g) was added and mixed with moderate agitation. The pH
is adjusted to approximately 5.4 with sulfuric acid (85%, 0.05 g)
and allowed to mix at moderate agitation. The suspending agent
(Attaflow FL, 1.67 g) was added and mixed with moderate agitation
Thickener (Rhodopol 23, 0.30 g) was slowly added with high
agitation and the suspension concentrate was further mixed for 30
minutes.
P.6--Preparation of Example 20
[0151] Step 1: In a suitably-sized vessel, polyarylphenol
alkoxylate phosphate (Soprophor 3D33, 35.13 g) and polyarylphenol
alkoxylate (Soprophor BSU, 34.74 g) were mixed to homogeneity.
Potable water (442.0 g), antifoam (Antifoam 1500, 2.22 g) and
potassium hydroxide (50% in water, 2.16 g) were further added with
mixing, followed by an active ingredient (D) (475.8 g). The crude
suspension was milled with a Netzsch Lab Mini Zeta IIE mill until
the particle size of the suspended particles is below 1.8
micrometers (X.sub.95) to yield a millbase of the active
ingredient.
[0152] Step 2: Thereafter, in a suitably-sized vessel, potable
water (80.0 g), polyarylphenol alkoxylate (Soprophor BSU, 40.4 g)
and propylene glycol (32.0 g) were added with high shear mixing via
a Silverson mixer (3.0 rpm) to homogeneity. Rape seed oil methyl
ester (Steposol ROE-W, 48.0 g) was added slowly to a Silverson
mixer at a rate of 3.5 rpm. Mixing continued at this rate for 4
minutes, resulting in particle size of 0.61 micrometers
(X.sub.95).
[0153] Step 3: Thereafter, in a suitably-sized vessel,
suspoemulsion prepared in Step 2 (62.57 g), potable water (25.75
g), preservative (Acticide GA, 0.19 g) and antifoam (Antifoam 1500,
0.17 g) were added with moderate agitation to homogeneity. Millbase
prepared in Step 1 (26.30 g) and Abamectin millbase (P.1, 4.28 g)
and suspending agent (Attaflow FL, 1.54 g) were added and mixed
with moderate agitation. Thickener (Rhodopol 23, 0.28 g) was slowly
added with high agitation. The suspension concentrate was further
mixed for 30 to 40 minutes or until homogeneous.
[0154] The remaining examples were prepared analogously with
appropriate adjustments to active ingredients, inert concentrations
and types, and particle sizes.
[0155] Examples J & K are commercial emulsifiable concentrates
of abamectin--Example J is the US product known as AGRIMEK and
Example K is the European product called VERTIMEC
TABLE-US-00001 TABLE 1 Examples of formulations (wt %) A 1 B 2 C D
3 4 Abamectin (component (A)) 8.24 8.24 8.00 8.00 4.00 4.03 4.02
4.01 a polyoxyalkylene-sorbitan ester having -- 16.67 -- 17.00 --
-- 16.91 17.00 an HLB of 15 (component (B)) a
polyoxyalkylene-sorbitan ester having -- -- -- -- -- -- -- an HLB
of 16 (component (B)) alkoxylated polyarylphenol (component 1.00
0.81 1.00 1.00 0.92 0.91 0.92 0.93 (C)) alkoxylated polyarylphenol
phosphate 1.48 1.25 1.50 1.50 1.38 1.39 1.36 1.38 (component (C))
antifreeze 4.95 4.95 5.02 5.00 4.59 4.58 4.58 4.57 antifoam 0.20
0.20 0.20 0.25 0.20 0.21 0.21 0.18 preservative 0.06 0.06 0.08 0.10
0.09 0.10 0.08 0.09 thickener 0.13 0.13 0.15 0.25 0.24 0.27 0.24
0.27 pH buffer 0.25 0.12 0.12 0.11 0.10 0.07 0.10 0.10 water
balance balance balance balance balance balance balance balance
Particle size, .times.50 of component A (.mu.m) 3.0 3.0 0.7 0.7
2.07 0.57 0.57 2.07 Particle size, .times.95 of component A (.mu.m)
12 12 1.5 1.5 9.87 1.35 1.35 9.87 Particle size, .times.50 of
formulation (.mu.m) 3.0 3.0 0.7 0.7 2.07 0.57 0.57 2.07 Ratio of
(B):(A) -- 2.0 -- 2.1 -- -- 4.3 4.3
TABLE-US-00002 TABLE 2 Examples of formulations (wt %) 5 6 7
Abamectin (component (A)) 4.02 4.00 8.0 a polyoxyalkylene-sorbitan
ester having an -- -- 17.00 HLB of 15 (component (B)) a
polyoxyalkylene-sorbitan ester having an 16.98 16.91 -- HLB of 16
(component (B)) alkoxylated polyarylphenol (component (C)) 0.90
0.92 -- alkoxylated polyarylphenol phosphate 1.39 1.38 --
(component (C)) Complex organic phosphate ester, free acid -- --
1.00 Block copolymer PO/EO -- -- 1.00 antifreeze 4.58 4.57 5.00
antifoam 0.20 0.20 0.21 preservative 0.08 0.10 0.11 thickener 0.24
0.24 0.25 pH buffer 0.08 0.08 0.11 water balance balance balance
Particle size, .times.50 of component A (.mu.m) 0.57 2.07 --
Particle size, .times.95 of component A (.mu.m) 1.35 9.87 1.5
Particle size, .times.50 of formulation (.mu.m) 0.57 2.07 -- Ratio
of (B):(A) 4.2 4.2 2.1
TABLE-US-00003 TABLE 3 Examples of formulations (wt %) 8 E 9 10 F
11 12 Abamectin (component (A)) 1.75 1.75 1.78 1.87 1.73 1.71 1.78
a polyoxyalkylene-sorbitan ester having 8.24 -- -- -- -- -- -- an
HLB of 15 (component (B)) Tall oil fatty acid having an HLB of 13
-- -- 20.22 -- -- -- -- (component B) Condensation product of
castor oil and -- -- -- 9.97 -- -- -- EO having an HLB of 13
(component B) a polyoxyalkylene-sorbitan ester having -- -- -- --
-- 8.33 -- an HLB of 13.3 (component (B)) a
polyoxyalkylene-sorbitan ester having -- -- -- -- -- -- 8.27 an HLB
of 16 (component (B)) alkoxylated polyarylphenol (component 1.84
10.11 -- -- 1.87 1.87 1.85 (C)) alkoxylated polyarylphenol
phosphate 2.00 0.06 -- -- 1.86 1.87 1.88 (component (C)) Rape seed
oil methyl ester (an oil) 12.13 -- -- Medium chain triglycerides
(an oil) -- -- 11.97 antifreeze 11.47 9.56 21.43 9.87 11.64 11.65
11.65 antifoam 0.23 0.15 0.13 0.17 0.26 0.29 0.26 preservative 0.26
0.19 0.26 0.24 0.25 0.28 0.32 thickeners 2.22 1.60 1.43 1.70 2.25
2.31 2.69 Base pH buffer 0.23 0.004 0.004 0.004 0.09 0.05 0.04 Acid
pH buffer -- 0.04 0.06 0.05 -- -- -- water balance balance balance
balance balance balance balance Particle size, .times.50 of
component A 0.57 0.57 0.57 0.57 0.57 0.57 0.57 Particle size,
.times.95 of component A 1.35 1.35 1.35 1.35 1.35 1.35 1.35
Particle size, .times.50 of formulation 0.57 0.57 0.57 0.57 0.57
0.57 0.57 Ratio of (B):(A) 4.7 -- 11.4 5.3 -- 4.9 4.6
TABLE-US-00004 TABLE 4 Examples of formulations (wt %) 13 14 15 16
G Abamectin (component (A)) 1.71 2.12 3.02 3.43 1.71 co-active
ingredient (component (D)) 4.29* 8.49* 13.85+ 6.86+ 4.29 a
polyoxyalkylene-sorbitan ester having an 8.00 8.00 17.00 17.00 --
HLB of 15 (component (B)) alkoxylated polyarylphenol (component
1.84 2.14 0.06 0.07 1.80 (C)) alkoxylated polyarylphenol phosphate
1.84 2.77 1.09 0.60 1.78 (component (C)) lignosulfonate 0 0 0.35
0.17 -- antifreeze 11.69 10.32 1.70 1.04 11.56 antifoam 0.29 0.30
0.20 0.12 0.28 preservative 0.25 0.25 0.25 0.25 0.25 thickener 0.19
0.19 0.15 0.16 0.19 pH buffer 0.08 0.11 0.30 0.31 0.08 suspension
aid 2.00 1.94 1.91 2.00 2.00 water balance balance balance balance
balance Particle size, .times.50 of Al (A) 0.5 0.5 0.5 0.5 0.5
Particle size, .times.95 of Al (A) 1.3 1.3 1.3 1.3 1.3 Particle
size, .times.50 of Al (D) 0.5 0.5 2.9 2.9 0.5 Particle size,
.times.95 of Al (D) 1.3 1.5 8.0 8.0 1.3 Particle size, .times.50
(formulation) 0.5 0.5 1.6 1.6 0.5 Ratio of (B):(A) 4.7 3.8 5.6 5.0
-- *chlorantraniliprole; + thiamethoxam
TABLE-US-00005 TABLE 5 Examples of formulations (wt %) 17 18 19 20
21 22 23 H Abamectin (component (A)) 1.71 1.75 1.75 1.75 1.75 1.75
1.75 1.75 Cyantraniliprole (component (D)) 5.98 8.75 8.75 8.75 8.75
8.75 8.75 8.75 a polyoxyalkylene-sorbitan ester having 20.04 20.13
20.14 -- -- -- 8.29 -- an HLB of 15 (component (B)) Tall oil fatty
acid having an HLB of 13 -- -- -- -- 20.05 20.32 -- -- (component
B) Condensation product of castor oil and -- -- -- 10.00 -- -- --
-- EO having an HLB of 13 (component B) a polyoxyalkylene-sorbitan
ester having -- -- -- -- -- -- -- -- an HLB of 13.3 (component (B))
a polyoxyalkylene-sorbitan ester having -- -- -- -- -- -- -- -- an
HLB of 16 (component (B)) alkoxylated polyarylphenol (component
0.53 0.77 0.79 0.79 0.78 0.79 2.57 11.00 (C)) alkoxylated
polyarylphenol phosphate 0.55 0.79 0.81 0.81 0.80 0.81 2.38 0.81
(component (C)) Rape seed oil methyl ester (an oil) -- -- -- -- --
-- -- 12.26 Medium chain triglycerides (an oil) -- -- -- 10.00 --
-- -- -- antifreeze 20.96 21.00 20.97 9.34 20.82 21.02 4.98 9.57
antifoam 0.17 0.18 0.23 0.14 0.18 0.18 0.31 0.18 preservative 0.20
0.25 0.24 0.23 0.24 0.23 0.23 0.21 thickeners 1.22 1.18 1.25 1.21
1.17 1.25 1.91 1.21 Base pH buffer 0.04 0.06 0.06 0..06 0.06 0.06
0.19 0.06 Acid pH buffer 0.05 0.10 0.02 0.45 0.09 0.29 0.02 0.02
water balance balance balance balance balance balance balance
balance Particle size, .times.50 of component A 0.57 0.57 0.57 0.57
0.57 0.57 0.57 0.57 Particle size, .times.95 of component A 1.35
1.35 1.35 1.35 1.35 1.35 1.35 1.35 Particle size, .times.50 of
component D 0.48 1.06 0.48 0.48 1.06 0.48 0.48 0.48 Particle size,
.times.95 of component D 1.80 11.80 1.80 1.80 11.80 1.80 1.80 1.80
Ratio of (B):(A) 11.7 11.5 11.5 5.7 11.5 11.6 4.7 --
[0156] Dilution Tests:
[0157] Dilution tests were carried out room temperature. Using an
Eppendorf pipette, 4 mL of each formulation was diluted into 96 mL
of water in a 100 mL glass graduated cylinder. The water having
different levels of water hardness, e.g. 50 ppm, 342 ppm and 1000
ppm corresponding to concentrations of divalent ions (namely
calcium and magnesium) was used. The time intervals were chosen to
simulate diluted product standing over a typical "break" for the
applicator (1, 2 or 4 hours) and overnight (24 hours). The
dilutions were inverted 20.times. and allowed to stand. After
standing for the desired time, the cylinders were noted for the
volume of settled sediment and after the 24 hour reading they were
subsequently subjected to cycles of inversions until the bottom of
each cylinder was visually free of sediment. Inversions were
performed manually (see Table X & Y for the results).
TABLE-US-00006 TABLE X Active ingredient (A) Water hardness
Sediment (mL) # reinversions Particle size for dilutions 1 4 24 %
after standing Example (D95/D50, in microns) (ppm)) Hour Hours
Hours serum overnight 3 1.35/0.57 50 -- -- -- -- 2 3 1.35/0.57 342
-- -- -- -- 2 3 1.35/0.57 1000 -- -- -- -- 2 4 9.87/2.07 50 -- --
-- 1.0 15 4 9.87/2.07 342 -- -- 0.5 1.5 11 4 9.87/2.07 1000 -- --
0.5 1.5 13 5 1.35/0.57 50 -- -- -- -- 7 5 1.35/0.57 342 -- -- -- --
4 5 1.35/0.57 1000 -- -- 0.25 -- 7 6 9.87/2.07 50 -- -- 0.5 1.0 8 6
9.87/2.07 342 -- -- 0.75 1.0 6 6 9.87/2.07 1000 -- trace 0.5 1.0 10
D 1.35/0.57 50 -- -- -- -- 10 D 1.35/0.57 342 -- -- -- -- 10 D
1.35/0.57 1000 -- -- -- -- 10 C 9.87/2.07 50 -- -- -- 1.0 14 C
9.87/2.07 342 -- -- 0.25 1.0 12 C 9.87/2.07 1000 -- -- 0.5 1.0
16
TABLE-US-00007 TABLE Y active active Water # ingredient (D)
ingredient hardness reinversions particle Size (A) particle for
Sediment, after (D95, D50 size (D95, in dilutions Sediment,
Sediment, overnight, standing Example in microns) microns) (ppm) 1
hr in mL 2 hr in mL in mL overnight 12 8.52, 1.07 1.16 50 nil nil
trace 22 12 8.52, 1.07 1.16 1000 trace trace 1.5 12 G 8.52, 1.07
1.16 50 trace trace trace 31 G 8.52, 1.07 1.16 1000 trace trace 0.5
12 12(2) 4.56, 0.69 1.16 50 nil trace trace 23 12(2) 4.56, 0.69
1.16 1000 nil 0.25 2.5 5 G(2) 4.56, 0.69 1.16 50 nil trace trace 20
G(2) 4.56, 0.69 1.16 1000 trace 0.25 3 9 12(3) 1.34, 0.17 1.16 50
nil nil trace 6 12(3) 1.34, 0.17 1.16 1000 nil nil 0.25 6 G(3)
1.34, 0.17 1.16 50 nil nil trace 8 G(3) 1.34, 0.17 1.16 1000 nil
trace 0.5 8 Note: Examples 12(2), 12(3) correspond compositionally
to Example 12 and Examples G(2) and (G3 correspond compositionally
to Example G, but the milling of the active ingredient (D)
composition varied before admixing with the composition containing
active ingredient (A).
Example B1--Translaminar Test Against Two Spotted Spider Mite
Tetranychus urticae on French Beans (Phaseolus vuloaris)
[0158] The underside of 2 week old bean plants was infested with a
mixed population of T. urticae. The border of the underside of the
leaves is surrounded with a gum barrier to prevent the mites to
move to the upper side of the leaves. One day after the infestation
plants were treated with a track sprayer from the top with 200 L/ha
of Example 2 products containing different amounts of Penetrator
Plus. Plants were incubated in the greenhouse for 9 days and the
evaluation was done on mortality against eggs and mobile stages
(see Table A for the results of ABA efficacy).
Example B2--Control of tetranychus sp. Adults on Vegetables
[0159] In a plot size of 14 m2, two foliar spray applications of
each composition were made at a treatment rate of 9 grams/ha
(second was 7 days after the first application). Each treatment was
done in three replicates. Each adjuvant was added to Example 1 in a
tank-mix based on 17 ml product/ha. First application was conducted
71 days after transplanting and the evaluation was done on
mortality against mobile stages by taking 20 leaves from each plot
at different intervals (see Table B for the results).
Example B3--Control of Colorado Potato Bettle on Potatoes
[0160] In a plot size of 7.5 m2, one foliar spray application of
each composition were made at a treatment rate of 1 grams/ha. Each
treatment was done in three replicates. Each adjuvant was added to
Example 1 in a tank-mix based on 2 ml product/ha. The application
was conducted 53 days after planting and the evaluation was done on
mortality against larvae by counting the live larvae present per
plot at different intervals and converting the data in % of control
(see Table C for the results).
Example B4: Control of Liriomyza trifolii pupae on
Chrysanthemums
[0161] CHRYSANTHEMUMS potted plants were infested with a very high
population of adult leafminers allowing them to lay eggs. Four days
after the initial infestation plants were sprayed using a CO2
compressed backpack sprayer with an application volume of 1800
L/ha. Plants were incubated in the greenhouse for 9 days after the
application and the evaluation was done by counting the number of
pupae per plant obtained for each treatment (see Table D for the
results).
Example B5: Residue Study
[0162] In a plot size of 25 ft.times.5 ft with 2 rows of Romaine
lettuce (30'' row spacing, 8'' plant spacing so .about.70
plants/plot), a single application of a treatment listed in Table
below was made as a post foliar broadcast spray at a rate of 0.038
lb. a.i. per acre. Each treatment was done in two replicates with a
control in each replicate. A minimum of .about.3 lb of lettuce
leaves were collected for each sample. Samples were harvested at 0,
0.25 (corresponding to 6hrs), 3, 7, 14 and 21 days after last
application (DALA). The 0-DALA samples were harvested as soon as
the spray dried. Samples were transported frozen and were prepared
by grinding the samples with dry ice using a tabletop mill. The
abamectin residue was analysed using a HPLC-Fluorescence Method
(see Table E for the results).
TABLE-US-00008 Treatment Application Application Type GPA 1 Control
-- -- 2 Example J Post foliar broadcast/on 29.5 (comparative) the
day of harvest of mature leaves 3 Example A Post foliar
broadcast/on 29.9 the day of harvest of mature leaves 4 Example 2
Post foliar broadcast/on 30.5 the day of harvest of mature leaves 5
Example J & Dyne- Post foliar broadcast/on 29.7 Amic .RTM. at
0.25% v/v the day of harvest of mature leaves 6 Example A &
Dyne- Post foliar broadcast/on 30.1 Amic .RTM. at 0.25% v/v the day
of harvest of mature leaves 7 Example 2 & Dyne- Post foliar
broadcast/on 29.9 Amic .RTM. at 0.25% v/v the day of harvest of
mature leaves
Example B6: UV Degradation Study
[0163] Photostability was assessed using an Atlas SUNTEST XLS+ unit
(Part number 55007820) which utilises a xenon arc-lamp and a
Special UV-filter (Part number 56052371) to simulate natural
sunlight in both spectrum and intensity.
[0164] Treatments were diluted either in ultra-pure water (or in
ultra-pure water containing 0.1% Penetrator Plus) to give dilutions
that were 125 ppm wrt abamectin. 8.times.2 ul drops were dispensed
using a Hamilton PB600 repeating dispenser fitted with a glass 100
.mu.l Hamilton syringe onto pre-scored glass microscope
slides--typically seven or eight for each treatment. These were
allowed to dry prior to being covered with clean UV transparent
silica slides to minimise volatile loss from the deposit. One slide
for each compound was not irradiated and designated as time zero
(T0). The other prepared slides were placed in the SUNTEST XLS+ on
a water-cooled sample table (attached to a circulating water bath
set to 15.degree. C.) and irradiated for time periods ranging from
30 minutes up to 43 hours.
[0165] To quantify the amount of compound remaining, one slide was
removed for each treatment from the SUNTEST unit, broken in half
across the shaft of a small spatula, sandwiched with the clean
sides together and placed in a 60 ml wide necked glass screw topped
jar. The silica slide was rinsed with 2.times.2.5 mls of 50:50
(80/20 MeCN/THF): 0.1% H3PO4 into the jar, the lid replaced and the
jar sonicated for 30 minutes. All jars were left standing at room
temperature in covered boxes prior to analysis by LC with MS
detection without further preparation (see Table F for the
results).
Example B7:
[0166] Two golden Delicious apple plants grown outside in a
propagation container (1-2 years old) were treated with the
products. The treatment areas for new and old leaves were defined
and marked before product application. A horizontal band was marked
on each leaf (approximately 3/4 of the way down from the leaf tip)
with a permanent marker pen. All treatments were applied using a
hand held pipette to the marked areas on each leaf as 10 .times.0.5
ul droplets (corresponding to 25 ug Al per leaf) with four
replicate leaves per treatment, and the plants left outside. The
products were AGRIMEK, Example 2, and Example 2 with 0.25% v/v
Horticultural spray oil (i.e summer oil). After 1, 3 and 6 days
after treatment, abamectin residues were assessed either on the
leaf surface or inside the leaf tissue on all four leaves per
product treatment. Surface analysis involved washing the leaf with
acetone, followed by a chloroform and then LCMS, while inside the
leaf tissue analysis involved freezing the leaves, homogenising in
5 ml acetone, centrifuging and 1 ml of the resulting supernatant
used for LCMS analysis (see Table G & H for the results).
TABLE-US-00009 TABLE A control of Tetranychus urticae ABA Varying
amounts of Penetrator Plus, based on %, v/v a.i ppm 0 0.05 0.1 0.2
12.5 35 100 100 100 3 0 97 100 100 0.8 0 40 96 100 0.2 0 0 47
97
TABLE-US-00010 TABLE B control of tetranychus sp. adults ABA
formulation, Adjuvant, 17 ml 3DAA1, 5DAA1, 7DAA1, 3DAA2, 7DAA2,
10DAA2, 15DAA2, 9 g Al/ha product/ha % % % % % % % Example K -- 75
75 61 83 79 78 74 (comparative) Example B -- 62 41 41 54 62 64 49
Example 2 -- 79 55 56 67 79 68 58 Example B ADIGOR 65 52 40 60 78
75 61 Example B SILWET L77 57 50 42 59 81 77 69 Example B ATLOX 58
54 41 63 77 71 67 SEMKOTE E-135 Example B ATPLUS 463 76 56 45 78 78
82 77
TABLE-US-00011 TABLE C control of Colorado potato battle ABA
formulation, Adjuvant, 2 ml 1DAA1, 3DAA1, 5DAA1, 7DAA1, 11DAA1, 9 g
Al/ha product/ha % % % % % Example K -- 100 97 74 66 35
(comparative) Example 2 -- 100 100 100 100 97 Example B ADIGOR 100
100 100 100 97 Example B SILWET L77 100 100 99 100 98 Example B
ATLOX SEMKOTE E-135 100 100 100 100 98 Example B ATPLUS 463 100 100
97 100 97 Example B ALKAMUL BR 100 100 100 100 97 Example B
TURBOCHARGE D 100 100 100 100 97 Example B TWEEN 80 100 100 98 100
95 Example B CET SPEED* 100 100 95 100 97 *applied at 10.1 ml
product/ ha
TABLE-US-00012 TABLE D control of Liriomyza Trifolii pupae 9DAA1, %
Example J (comparative) 52 Example A 0 Example 1 21 Example B 16
Example 2 44
TABLE-US-00013 TABLE E recovered abamectin (ppb) Abamectin (ppb) Ex
J & Ex. A & Ex. 2 & Interval Dyne- Dyne- Dyne- (DALA)
Ex. J Ex. A Ex. 2 Amic .RTM. Amic .RTM. Amic .RTM. 0 301 319 407
313 402 397 0.25 192 340 347 203 195 133 3 63 192 228 99 94 110 7
16 112 143 39 72 38 14 9 52 53 12 37 22 21 6 62 48 9 40 11 Note:
Residues reported above represent the average of two replicates
expressed as Abamectin B1a (avermectin B1a and its 8,9-Z isomer)
plus Abamectin Bib No residues (<2.00 ppb) were detected in any
of the controls analyzed during this study.
TABLE-US-00014 TABLE G micrograms of abamectin inside the leaf
tissue Time Example K Example 2 Example 2 + oil* 0 0.22 0.24 0.39 1
0.23 0.23 0.45 3 0.15 0.14 0.13 6 0.33 0.16 0.33 *oil is
Horticultural spray oil, i.e. summer oil
TABLE-US-00015 TABLE H T micrograms of abamectin on the leaf
surface Time Example K Example 2 Example 2 + oil* 0 12.87 12.54
7.74 1 8.91 12.57 4.58 3 1.19 7.65 2.65 6 0.77 4.10 2.02 *oil is
Horticultural spray oil, i.e. summer oil
* * * * *