AU2021103392A4 - Pesticide formulation comprising spinosad and s-methoprene - Google Patents
Pesticide formulation comprising spinosad and s-methoprene Download PDFInfo
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- AU2021103392A4 AU2021103392A4 AU2021103392A AU2021103392A AU2021103392A4 AU 2021103392 A4 AU2021103392 A4 AU 2021103392A4 AU 2021103392 A AU2021103392 A AU 2021103392A AU 2021103392 A AU2021103392 A AU 2021103392A AU 2021103392 A4 AU2021103392 A4 AU 2021103392A4
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- formulation
- surfactant
- methoprene
- spinosad
- solvent
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- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IXKCDYCGOZFZFK-UHFFFAOYSA-N calcium;dodecylbenzene Chemical compound [Ca].CCCCCCCCCCCCC1=CC=CC=C1 IXKCDYCGOZFZFK-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- HQSBWLQFLLMPKC-UHFFFAOYSA-N dodeca-2,4-dienoic acid Chemical compound CCCCCCCC=CC=CC(O)=O HQSBWLQFLLMPKC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229930014550 juvenile hormone Natural products 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 150000003633 juvenile hormone derivatives Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000004535 oil miscible liquid Substances 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- SRJQTHAZUNRMPR-UHFFFAOYSA-N spinosyn A Natural products CC1C(=O)C2=CC3C4CC(OC5C(C(OC)C(OC)C(C)O5)OC)CC4C=CC3C2CC(=O)OC(CC)CCCC1OC1CCC(N(C)C)C(C)O1 SRJQTHAZUNRMPR-UHFFFAOYSA-N 0.000 description 1
- RDECBWLKMPEKPM-UHFFFAOYSA-N spinosyn D Natural products CC1C(=O)C2=CC3C4CC(OC5C(C(OC)C(OC)C(C)O5)OC)CC4C(C)=CC3C2CC(=O)OC(CC)CCCC1OC1CCC(N(C)C)C(C)O1 RDECBWLKMPEKPM-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- QVLMUEOXQBUPAH-UHFFFAOYSA-N stilben-4-ol Chemical class C1=CC(O)=CC=C1C=CC1=CC=CC=C1 QVLMUEOXQBUPAH-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004548 suspo-emulsion Substances 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
- A01N63/30—Microbial fungi; Substances produced thereby or obtained therefrom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Insects & Arthropods (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a pesticide formulation comprising spinosad, s
methoprene, a surfactant and a solvent, wherein the formulation is an emulsifiable
concentrate, an emulsion or an ultra low volume (ULV) liquid, as well as methods
5 for producing a pesticide formulation and use of a pesticide formulation.
Description
This invention relates to a pesticide formulation. In particular, the
present invention relates to a pesticide formulation containing spinosad and
s-methoprene as active agents and to methods of preparing and using said
formulation. In preferred embodiments, the formulation is a concentrate for
dilution and subsequent application to stored grains as a protectant against
insecticidal attack. However, it will be appreciated that the invention is not
limited to this particular field of use.
Spinosad is a 'natural' or 'bio-' insecticide being derived by the
fermentation of a species of the actinomycete fungus, Saccharopolyspora
spinosa. It is mixture of spinosyns A and D and was discovered and
developed originally by Elanco, now Dow AgroSciences, for the control of a
variety of insect pests, including: Lepidoptera, Diptera, Thysanoptera, some
Coleoptera, termites and ants, on a wide range of crops, including: cotton,
fruit (pome, stone and field), vegetables, wheat and tobacco, and is also
used on turf and ornamentals with its first marketplace introduction in USA
in 1997. Spinosad is highly active by both contact and ingestion, and
primarily targets binding sites on nicotinic acetylcholine receptors, leading
to a disruption in acetylcholine neurotransmission. The actual physiological
effect of spinosad varies between insect species and life stages. For
instance, it affects certain species in the adult stage, and other species in the larval stage. Spinosad a mixture of spinosyn A
(2R,3aR,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-2,3,4-tri-O-methyl
alpha-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy
beta-D-erythopyranosyloxy)-9-ethyl
2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexadecahydro-14-methyl
1H-8-oxacyclododeca[b]as-indacene-7,15-dione; CAS#131929-60-7)and
spinosyn D (2S,3aR,5aS,5bS,9S,13S,14R,16aS,16bS)-2-(6-deoxy-2,3,4
tri-O-methyl-alpha-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6
tetradeoxy-beta-D-erythopyranosyloxy)-9-ethyl
2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexadecahydro-4,14
dimethyl-1H-8-oxacyclododeca[b]as-indacene-7,15-dione; CAS# 131929
63-0) in the proportion about 50-95% to about 50-5%.
S-methoprene (isopropyl (E,E)-(7S)-11-methoxy-3,7,11-trimethyl
2,4-dodecadienoate; CAS: 65733-16-6) is an enantiomer of methoprene
and is known to be an insect growth regulator, particularly a juvenile
hormone mimic, which prevents metamorphosis of juvenile larvae to viable
adults. S-methoprene controls many insect pests (especially Diptera and
Pharaoh's ants, but also Coleoptera, Homoptera and Siphonaptera) in
public health, stored commodities (including tobacco), food handling,
processing and storage establishments, mushroom houses, on animals,
and on plants (including glasshouse plants). Particular uses include control
of mosquito larvae; sciarid flies in mushroom houses; cigarette beetles and
tobacco moths in stored tobacco; Pharaoh's ants; leaf miners on glasshouse
chrysanthemums; stored product pests in food and tobacco processing plants and warehouses.
It is a known problem that insecticides, such as spinosad and s
methoprene, when administered alone, can display reduced efficacy in
populations of target pests that are treated multiple times, as the
populations tend to build resistance to the active ingredient. One approach
to counteract such resistance is to combine active ingredients that have
different mechanisms of action. Accordingly, it would be preferable, and a
significant advance in the art, to provide a combination pesticide
composition that does not display reduced efficacy over time or with
repeated exposure to a target population.
Notwithstanding the commercial availability of a range of
formulations comprising spinosad and/or s-methoprene, there remains a
need for improved combination formulations comprising spinosad and s
methoprene for use in agriculture and/or industry that overcomes one or
more of the inherent limitations of commercially available formulations
comprising spinosad and/or s-methoprene.
It is an object of the present invention to overcome or ameliorate at
least one of the disadvantages of the prior art, or to provide a useful
alternative.
In a first aspect, the invention provides a pesticide formulation
comprising:
spinosad;
s-methoprene; a surfactant; and a solvent, wherein the formulation is an emulsifiable concentrate, an emulsion or an ultra low volume (ULV) liquid.
In some embodiments, the spinosad is present at a concentration of
at least about 5 g/L of the total weight of the formulation. Particularly, the
spinosad and s-methoprene can be present in an amount between about 5
g/L to about 150 g/L each.
In certain embodiments, the s-methoprene is present at a
concentration of at least about 5 g/L of the total weight of the formulation.
Particularly, the s-methoprene can be present in an amount between about
5 g/L to about 150 g/L.
In some embodiments, the surfactant is selected from a non-ionic
surfactant, an anionic surfactant or a mixture thereof, and is present in an
amount of at least 50 g/L. Particularly, the surfactants present are in a total
concentration of between about 50 g/L and about 150 g/L. In some
embodiments, the composition may comprise a mixture of a non-ionic
surfactant and an anionic surfactant. The ratio of non-ionic surfactant to
anionic surfactant may be between 5:1 and 1:5. Preferably, the ratio may
be between 1:2 and 2:1, or about 1:1.
Suitably, the surfactant may be selected from the group consisting of
an alkylphenol, an alkylbenzene sulphonate, an alkoxylated styryl phenol, a
vegetable oil ethoxylate, a polyoxyalkylenesorbitan monolaurate and any
combination thereof. Preferably, the surfactant is selected from the group consisting of calcium C10-16 alkylbenzyl sulphonate, an ethoxylated tristyryl phenol, a castor oil ethoxylate, a polyoxyethylenesorbitan monolaurate or combinations thereof.
The total amount of solvent present in the emulsifiable concentrate
formulation may be at least 650 g/L, or between about 650 g/L and about
1100 g/L. In certain embodiments, the solvent comprises methyl salicylate.
The solvent may be a solvent substantially or entirely comprising synthetic
methyl salicylate or it may be an organic extract of Oil of Wintergreen. The
solvent may also comprise a further solvent that is miscible with methyl
salicylate, such as N-methylpyrrolidone.
When additional solvents are used (i.e., in addition to the solvent
comprising methyl salicylate), each may be selected from the group
consisting of another petroleum derivative, a carboxamide, a benzoate, a
ketone, a pyrrolidone and any combination thereof. Preferably, the
additional solvent is selected from the group consisting of an alternative
heavy aromatic solvent naphtha (petroleum) distillate or N-methyl
pyrrolidone. More specifically, in one embodiment, the solvent comprises
methyl salicylate and N-methyl pyrrolidone.
In a second aspect, the present invention provides a pesticide
composition, comprising:
spinosad at a concentration of at least about 100 g/L;
s-methoprene at a concentration of at least about 100 g/L;
a non-ionic surfactant comprising a polyoxyethylenesorbitan
monolaurate; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate, wherein the ratio of non-ionic surfactant to anionic surfactant is
1:1; and
a solvent comprising methyl salicylate,
wherein the formulation is an emulsifiable concentrate.
In a third aspect, the present invention provides a method of
producing a pesticide formulation of the first or second aspect, comprising
the steps of (a) combining the spinosad, s-methoprene, a surfactant and a
solvent, and (b) mixing to form a pesticide formulation.
In a fourth aspect, the present invention provides a method of
preventing and/or controlling a pest infestation in a storage area,
comprising:
mixing the pesticide formulation of the first or second aspects with
water or a water-containing liquid to obtain a pesticide composition, and
applying the pesticide composition to a material for storage in the
storage area to thereby prevent and/or control the pest infestation,
wherein the material for storage is selected from the group consisting
of grain, fruit, vegetables and timber.
Suitably, the mixing step and/or the applying step in the method of
the third or fourth aspects may utilise any suitable equipment or mode for
carrying out these steps. For example, the mixing step may be carried out
by stirring or agitation, and the applying step may be carried out by spraying.
As used herein, except where the context requires otherwise, the
term "comprise" and variations of the term, such as "comprising",
"comprises" and "comprised", are not intended to exclude further elements,
components, integers or steps but may include one or more unstated further
elements, components, integers or steps.
It will be appreciated that the indefinite articles "a" and "an" are not to
be read as singular indefinite articles or as otherwise excluding more than
one or more than a single subject to which the indefinite article refers. For
example, "a" surfactant includes one surfactant, one or more surfactants
and a plurality of surfactants.
There is an advantage in providing pesticide products in a liquid form
as a concentrate having a relatively high concentration of active ingredient/s
in proportion to other excipients within the formulation and which are stable
in concentrate form but readily dispersible in water or a water-containing
liquid when diluted for use. By way of example, using a concentrate liquid
formulation allows for the treatment of a given volume of produce or target
area (e.g., crop, land, stored commodity, commercial or residential premises
etc.) with a reduced amount of the concentrated pesticide product being
used. As such, concentrated pesticide products afford a broadly better
economic outcome together with reduced costs (e.g., reduced non-active
ingredients, packaging, handling, storage, freight, labour, regulatory
licensing and disposal costs) and less environmental impact (e.g., reduced
non-active ingredients, such as solvents, surfactants, preservatives, anti
oxidants, dyes and consumption deterrents, and packaging, such as containers, closures, labels/booklets, pallets and pallet liners/boxes/wrapping).
In addition to the above, providing an emulsifiable concentrate,
emulsion-in-water or an ultra-low volume (ULV) liquid form of a pesticide
product can further alleviate some or all of the deficiencies of other product
formulations or preparations of the pesticide in question, such as
suspensions or suspoemulsions. To this end, in emulsifiable concentrate,
emulsion-in-water or ULV liquid formulations, the active ingredient is not in
the solid phase but is dissolved in a liquid phase, and thereby is not subject
to settling or physical phase separation of solid from liquid. This issue may
be seen in other commercially available combinations of spinosad and s
methoprene which are formulated as a suspoemulsion concentrate.
The selection of appropriate solvents and other excipients typically
requires careful consideration so as to achieve a passable emulsifiable
concentrate, emulsion-in-water or ULV liquid formulation with good stability,
acceptable shelf life and the desired dispersibility of the formulation in water
or a water-containing liquid before use. However, additional commercial
factors also need to be taken into consideration during product development
and when selecting solvents and other excipients for emulsifiable
concentrate, emulsion-in-water or ULV liquid formulations. These factors
may include: cost of the solvents and excipients and if a cheaper alternative
is available that is of comparable effectiveness (for instance, whether a
pure, synthetic solvent is necessary, or if a cheaper, less-pure organic extract could be used); and any environmental impact of the solvents and excipients.
In view of the foregoing, the present invention advantageously
provides a pesticide formulation comprising spinosad and s-methoprene in
combination, formulated as an emulsifiable concentrate, emulsion-in-water
or ULV liquid, that is suitable for the prevention, control or treatment of a
range of pest infestations in an agricultural, horticultural, industrial or
domestic setting. Advantageously, the pesticide formulations of the present
invention include methyl salicylate as a substantial component of the
solvent, either as a high purity synthetic methyl salicylate (CAS No. 119-36
8) or as an oily extract of the herb wintergreen, otherwise known as Oil of
Wintergreen (CAS No. 68917-75-9). The inventors have surprisingly found
that not only does methyl salicylate result in a stable emulsifiable
concentrate formulation comprising spinosad and s-methoprene, and hence
an enduring alternative to other commercially available combination
formulations, but methyl salicylate is understood to also provide
compounding insecticidal benefits to extend efficacy as a protectant of
stored grains.
In one embodiment, formulations described herein may be suitable
for application to stored grains as a protectant against insecticidal attack.
Further, the combination formulations are preferably an emulsifiable
concentrate.
Accordingly, in one broad form the invention resides in a pesticide
formulation comprising: spinosad; s-methoprene; a surfactant; and a solvent, wherein the formulation is an emulsifiable concentrate, an emulsion or an ultra low volume (ULV) liquid.
The term "spinosad" as used herein refers specifically to the mixture
of spinosyns A and D, which are derived from the fermentation of a species
of the actinomycete fungus, Saccharopolyspora spinosa. Spinosad is
known to act on affected insects neurologically, by disrupting acetylcholine
neurotransmission and hyperexcitation of the insect's nervous system.
The term "s-methoprene", or just "methoprene" refers to the 'S'
enantiomer of methoprene (propan-2-yl (2E,4E)-11-methoxy-3,7,11
trimethydodeca-2,4-dienoate), which is known to be a juvenile hormone
anolog. The'R'enantiomer is not believed to be active. Whilst s-methoprene
is not fatal to the affected insect, it does inhibit the insect from maturing to
the adult stage and hence unable to reproduce.
As will be shown herein, it is understood that the concentrate
formulations of the present invention are stabilized, at least in part, as a
result of the interaction between the surfactant(s) and solvent(s) present
within the formulations. The surfactant(s) and solvent(s) advantageously
and surprisingly provide an end product that achieves and maintains
homogeneity after manufacture and during storage, even at the equivalent of up to two years of storage under accelerated conditions, even though the active constituents are at or near their solubility limits.
The solvent of the pesticide formulations herein may comprise one
solvent, or they may comprise two or more solvents. It is understood that
the solvents of the formulation dissolves both active agents (the spinosad
and the s-methoprene), either alone or in combination with at least one
surfactant. In some embodiments, the solvent may comprise, or
substantially comprise, or contain, methyl salicylate. In some embodiments,
the solvent may also comprise water. Each solvent may be aprotic (i.e., they
are unable to donate a hydrogen atom). Each solvent may be polar or they
may be non-polar. In some embodiments, an emulsion may be formed
between a polar solvent and a non-polar solvent, or between a polar
solvent/water mixture and a non-polar solvent. The emulsion may be
stabilised by, or formed with, a surfactant, or more than one surfactants.
The surfactant of the pesticide formulations herein may comprise one
surfactant, or they may comprise two or more surfactants. The surfactant
may be an anionic surfactant, or it may be a non-ionic surfactant. In one
embodiment, the surfactant of the present invention may comprise both an
anionic surfactant and a non-ionic surfactant. It is understood that a
surfactant comprises a hydrophobic portion and hydrophilic portion,
whereby an anionic surfactant has a negative charge on the hydrophilic
portion, and a non-ionic surfactant has no formal charge. Anionic
surfactants are regularly obtained as a salt with a metal cation, such as a
sodium, potassium or calcium salt. It is expected that any surfactant suitable for use in pesticide formulations generally may be suitable for use in the formulations of the present invention. Suitable surfactants may be mixtures.
They may be proprietary products.
It is envisaged that the pesticide formulation may take the form of any
suitable liquid formulation known in the art. Exemplary liquid formulations
include oil-miscible liquids, ultra-low-volume (ULV) liquids, emulsifiable
concentrates, emulsions including oil-in-water and micro-emulsions.
In one particular embodiment, the pesticide formulation is or
comprises an emulsifiable concentrate.
It will be well understood that the term "emulsifiable concentrate
formulation" or "emulsifiable concentrate" (EC) refers to a homogenous
liquid formulation or concentrate of one or more active agents, such as a
pesticide, which, on dilution in water or a water-containing liquid, forms an
emulsion such as a spontaneous milky white emulsion comprising a
dispersed water immiscible phase. By way of example, a water insoluble
active ingredient is typically dissolved in a largely water insoluble solvent
that, upon combination and agitation with water, a water-containing liquid,
or the like, forms an emulsion being a distribution of droplets of the water
insoluble solvent and active ingredient amongst a water matrix stabilised by
surfactants. The term "emulsion", as used herein, refers to a fine dispersion
of minute droplets of one liquid in another in which it is not soluble or
miscible and includes microemulsions and macroemulsions.
In one aspect, the invention provides a pesticide formulation,
wherein: the spinosad is present at a concentration of at least about 5 g/L, or between about 5 g/L and about 150 g/L, of the total weight of the formulation; the s-methoprene is present at a concentration of at least about 5 g/L, or between about 5 g/L and about 150 g/L, of the total weight of the formulation; the surfactant is selected from a non-ionic surfactant, an anionic surfactant or a mixture thereof, and is present in an amount of at least 50 g/L, or between about 50g/L and about 150 g/L; and wherein the solvent is present in an amount of at least 350 g/L of the total volume of the formulation and comprises methyl salicylate, wherein the formulation is an emulsifiable concentrate.
In another aspect, the invention provides a pesticide concentrate,
comprising:
spinosad at a concentration of at least about 100 g/L;
s-methoprene at a concentration of at least about 100 g/L;
a non-ionic surfactant comprising a polyoxyethylenesorbitan
monolaurate;
an anionic surfactant comprising a calcium salt of an alkylbenzene
sulfonate, wherein the ratio of non-ionic surfactant to anionic surfactant is
1:1; and
a solvent comprising methyl salicylate,
wherein the formulation is an emulsifiable concentrate.
The statements which follow apply equally to the aforementioned aspects of the invention.
For the present invention, spinosad and s-methoprene are suitably
present in a concentration (e.g., at least about 5 g/L each) that provides a
concentrated pesticide formulation, particularly an emulsifiable concentrate
formulation, suitable for use in the effective prevention, control and/or
treatment of a pest infestation.
In relation to liquid pesticide formulations, such as emulsifiable
concentrate, emulsion-in-water or ULV liquid formulations, spinosad may be
present in an amount from about 5 g/L to about 150 g/L or any range therein
such as, but not limited to, about 10 g/L to about 100g/L, about 20 g/L to
about 50 g/L, about 40 g/L to about 120 g/L, about 50 g/L to about 125 g/L,
or about 25 g/L to about 40 g/L of the liquid pesticide formulation. In
particular embodiments of the present invention, spinosad is present in an
amount of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,
22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,
42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100,
105, 110, 115, 120, 125, 130, 135, 140, 145, 150 g/L, or any range therein,
of the liquid pesticide formulation. In certain embodiments of the present
invention, spinosad is present in an amount of about 10 g/L, about 50 g/L,
or about 100 g/L of the liquid pesticide formulation.
Further, in the liquid pesticide formulations of the present invention,
s-methoprene may also be present in an amount from about 5 g/L to about
150 g/L or any range therein such as, but not limited to, about 10 g/L to
about 1OOg/L, about 20 g/L to about 50 g/L, about40 g/L to about 120 g/L, about 50 g/L to about 125 g/L, or about 25 g/L to about 40 g/L of the liquid pesticide formulation. In particular embodiments of the present invention, s methoprene is present in an amount of about 5, 6, 7, 8, 9, 10, 11, 12, 13,
14,15, 16,17, 18, 19,20,21, 22,23, 24, 25,26, 27,28,29, 30,31, 32,33,
34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,55,60,65,
70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145,
150 g/L, or any range therein, of the liquid pesticide formulation. In certain
embodiments of the present invention, s-methoprene is present in an
amount of about 10 g/L, about 50 g/L, or about 100 g/L of the liquid pesticide
formulation. The ratio of the total amount of spinosad to s-methoprene may
be between about 10:1 and about 1:10 or any range therein, such as
between 10:1 and 1:5, or it may be about 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1,
3:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1 1:1.1,
1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7,
1:8, 1:9, 1:10, or any range therein in the liquid pesticide formulation. In
certain embodiments of the present invention, the ratio of spinosad to s
methoprene may be between 1:5 and 5:1, or more preferably be about 1:1.
The term "solvent" refers to any liquid capable of maintaining another
substance in solution. The solvent may comprise an alkyl salicylate, a
carboxamide having an amidoalkyl structure (i.e., R-CO-NR'R" structure
wherein R, R' and R" are independent an organic moiety or hydrogen)
inclusive of lactams and pyrrolidones, such as N-substituted pyrrolidones
(e.g., N-methyl pyrrolidone, N-butylpyrrolidone and N-octylpyrrolidone),
N,N-dimethylformamide and N,N-dimethylacetamide, an acetic acid C6-C8 branched alkyl ester (including the material sold under the trade name
Exxate 700), a ketone inclusive of cyclic ketones, aromatic ketones,
alkylketones (e.g., isophorone) and arylketones (e.g., acetophenone), a
benzoate, inclusive of alkyl benzoates (e.g., methyl benzoate, ethyl
benzoate), cyclohexanone, acetone, glycols, inclusive of glycol ethers such
as diethylene glycol monomethyl ether (including the material sold under
the trade name Carbitol), ethylene glycol monobutyl ethers (including the
material sold under the trade name Butyl Glysolv), propylene glycol
monomethyl ether (including the material sold under the trade name Glysolv
PM), methanol, ethanol, isopropanol, decanol and paraffins.
In one particular embodiment, the solvent comprises, or is, methyl
salicylate. More particularly, the solvent may be synthetic methyl salicylate
or an extract of Oil of Wintergreen. In some embodiments, the solvent may
also comprise a pyrrolidone, such as N-methyl pyrrolidone. In preferred
embodiments, the solvent may comprise both methyl salicylate and N
methyl pyrrolidone.
Such solvents may be used in isolation or in combination as a mixture
of two, three, four, five or more solvents. In one particular embodiment, the
solvent comprises first and second solvents. It will be appreciated that the
first and second solvents may be or comprise any solvent known in the art,
including water.
For the present aspect, the ratio of the first solvent to the second
solvent may suitably be between 1 and 20 parts of the first solvent, and
about 1 part of the second solvent. For example, the ratio may be about
20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1,
6:1, 5:1, 4:1, 3:1, 2:1, 1:1 and any range therein. In one preferred
embodiment, the ratio of the first solvent to the second solvent is about 1:1.
For the above aspects, the solvent of a liquid pesticide formulation,
including an emulsifiable concentrate, emulsion-in-water or ULV liquid
formulation of the present invention, may be present in a total amount from
about 350 g/L to about 1100 g/L or any range therein such as, but not limited
to, about 350 g/L to about 800 g/L, about 500 g/L to about 650 g/L, or about
400 g/L to about 1100 g/L of the liquid pesticide formulation. In particular
embodiments of the present invention, the solvent is present in an amount
ofabout 350, 360, 370, 380, 390, 400,410,420, 430, 440,450, 460, 470,
480,490,500,510,520,530,540,550,560,570,580,590,600,610,620,
630,640,650,660,670,680,690,700,710,720,730,740,750,760,770,
780,790,800,810,820,830,840,850,860,870,880,890,900,910,920,
930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040, 1050,
1060, 107, 1080, 1090, 1100 g/L, or any range therein, of the liquid pesticide
formulation. In certain embodiments of the present invention, the solvent is
present in an amount of at least about 350 g/L of the liquid pesticide
formulation. More particularly, the solvent is present in an amount ranging
between about 790 g/L to about 1080 g/L of the liquid pesticide formulation.
Further to the above, the solvent provided herein is preferably an
agriculturally acceptable solvent. The term "agriculturally acceptable
solvent" as used herein refers to a solvent that is not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user or others that may be exposed to the solvent when used as described herein.
As used herein, the term "surfactant" or surface-active agent refers
to an agent, usually an organic chemical compound that is at least partially
amphiphilic (i.e., typically containing a hydrophobic tail group and
hydrophilic polar head group). Given their structure, surfactants are
generally capable of lowering the surface tension (or interfacial tension)
between two liquids or between a liquid and a solid. Further to this, these
properties typically allow solubility of the surfactant in organic solvents as
well as in water, and allow the surfactant to promote solubilization or at least
dispersal of fatty/waxy materials in water and water-containing solutions. In
this regard, a surfactant may act as a detergent, a wetting agent, an
emulsifying agent, a foaming agent, a solubilising agent and/or a dispersing
agent.
Accordingly, in particular embodiments, the surfactant is or
comprises an emulsifying agent. As generally used herein, the term
"emulsifying agent" or "emulsifier" refers to a chemical agent, compound, or
substance capable of producing an emulsion by reducing the interfacial
tension between the two insoluble liquids. In some embodiments, the
surfactant may be a solubilising agent and act as a solvent in the
formulations described herein. In such embodiments, the surfactant may
replace at least a portion of the solvent required to form a stable formulation.
Similar to that for the solvents provided above, the surfactant
provided herein is preferably an agriculturally acceptable surfactant. The term "agriculturally acceptable surfactant" as used herein refers to a surfactant that is not unacceptably damaging to a plant and/or its environment, and/or not unsafe to the user or others that may be exposed to the surfactant when used as described herein.
The surfactant, including one or a plurality of surfactants (e.g., 1, 2,
3, 4, 5 etc. surfactants), are suitably present in a high enough concentration
that allows for the production of a combination pesticide formulation
comprising spinosad and s-methoprene, such as an emulsifiable
concentrate, emulsion-in-water or ULV liquid formulation. In this regard, it
will be apparent that an amount of the surfactant of the pesticide formulation
can vary, for example, depending on the specific form of the pesticide
formulation (e.g., liquid or solid formulation), the particular active ingredient
concentrations and the particular surfactant to be included therein.
With regard to liquid pesticide formulations, such as emulsifiable
concentrate, emulsion-in-water or ULV liquid formulations, the surfactant
may be present in a total amount of surfactant from about 50 g/L to about
150 g/L or any range therein such as, but not limited to, about 75 g/L to
about 100 g/L, or about 60 g/L to about 90 g/L thereof. In particular
embodiments of the present invention, the surfactant is present in an
amount of about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115,
120, 125, 130, 135, 140, 145, 150 g/L, or any range therein, of the liquid
pesticide formulation. In certain embodiments of the present invention, the
surfactant is present in an amount of at least about 60 g/L of the liquid
pesticide formulation. More preferably, the surfactant is present in an amount ranging between about 60 g/L to about 95 g/L of the liquid pesticide formulation.
For the present invention, the surfactant is suitably selected from the
group consisting of non-ionic surfactants, anionic surfactants, cationic
surfactants, zwitterionic surfactants, cation-anion composite surfactants
and any combination thereof. Suitable non-ionic surfactants may include an
alkoxylated styryl phenol, polyoxyethylene alkyl ethers, polyoxyethylene
alkyl phenyl ethers, polyoxyethylene polyoxypropylene ethers,
polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters,
polyoxyethylene polyoxypropylene block copolymers, sorbitan alkyl esters,
higher fatty acid alkanolamides and any combination thereof. Suitable
cationic surfactants may include alkylbenzene sulphonate salts, alkylamine
salts, quaternary ammonium salts and combinations thereof. Further,
suitable anionic surfactants may include naphthalenesulfonic acid
polycondensate, alkenylsulfonate, naphthalenesulfonate, formalin
condensate of a naphthalenesulfonate, formadehyde condensate of an
alkylnaphthalenesulfonate, lignin sulfonate, alkylarylsulfonate, alkylaryl
sulfonate sulfate, polystyrene sulfonate, polycarboxylate,
polyoxyethylenealkyl ether sulfate, polyoxyethylenealkylaryl ether sulfate,
alkylsulfosuccinate, alkyl sulfate, alkyl ether sulfonate, a higher fatty acid
alkali salt and any combination thereof.
In certain preferred embodiments, the one or more surfactants to be
included in the pesticide formulation, including the emulsifiable concentrate,
emulsion-in-water or ULV liquid formulations described herein, may comprise an anionic surfactant. As generally used herein, the term "anionic surfactant" refers to a surfactant comprising, as ionic or ionizable groups, only anionic groups. Such anionic groups may include, for example, -CO2H,
-C02-, -SO3H, -S03-, -OSO3H, -OS03-, -H2PO3, -HP03-, -P03 2-, -H2PO2,
=HPO2, -HP02-, =P02-, =POH, and =PO- groups. Suitable anionic
surfactants may include those hereinbefore described. Such anionic
surfactants may be used alone or in combination as a mixture of two, three,
four, five or more anionic surfactants. In certain embodiments, the one or
more surfactants to be included in the pesticide formulation, including the
emulsifiable concentrate, emulsion-in-water or ULV liquid formulations
described herein, may comprise a non-ionic surfactant. As generally used
herein, the term "non-ionic surfactant" refers to a surfactant that does not
contain or comprise an ionic or ionizable group. Suitable non-ionic
surfactants may include those hereinbefore described. Such non-ionic
surfactants may be used alone or in combination as a mixture of two, three,
four, five or more non-ionic surfactants. In certain embodiments, the
surfactant may comprise a combination of one or more anionic surfactant
and one or more non-ionic surfactant. In such embodiments, the ratio by
weight of total anionic surfactant to total non-ionic surfactant may be
between about 10:1 and about 1:10, or between 5:1 and 1:15, or between
5:1 and 1:5, or between 3:1 and 1:1, or between 2:1 and 1:2, or between
2:1 and 1:3, or about 1:1 or any range therein, or it may be about 10:1, 9:1,
8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1,
2.1:1, 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1,
1:1.1, 1:1.2, 1:1.3, 1:1.4:, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2,
1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9,
1:10, or any range therein, in the liquid pesticide formulation.
It will be appreciated that the surfactant may be any suitable
surfactant known in the art. Exemplary surfactants include an alkylphenol
alkoxylate (e.g., Termul 200), a polyoxyalkylene ether (e.g., Termul 203), an
alkoxylated oil (e.g., 36 x ethoxylated (e.g., Termul 1284); -54 x ethoxylated
(e.g., Termul 1285)), an alkylphenol alkoxylate (e.g., -10 x ethoxylated (e.g.,
TericN10)), an alkoxylated alcohol (Alcohol C12 - C15, -23 x ethoxylated
(e.g. Teric 12A23); Alcohol C12, -3 x ethoxylated (e.g. Surfactant 12A3)),
an alkoxylated polyaryl phenol (e.g., Tristyryl Phenol, -16 x ethoxylated
(e.g. TSP15, Termul 3150), an alkoxylated block co-polymer (Ethoxylate
Propoxylate copolymer (e.g. Teric PE64)), an alkylbenzenesulphonate
(e.g., Calcium C10-16 alkylbenzyl sulphonate, branched or linear chain in
solvent (e.g. Ninate 60E, NANSA EVM70/2E, Kemmat HF60)), a
polysorbate (e.g., Tween 20); an alcohol ether sulphate (e.g. Toximul
TANS-5), an alkylamine ethoxylate (e.g. Toximul TAABS-5), a silicone
polymer, inclusive of polysiloxanes (e.g., Evonik Break-Thru OE 446, Evonik
Break-Thru AF 9903, Jiangxi Tiansheng QS-302) and silicone glycol
copolymers (e.g., Xiameter OFX-5211), a block co-polymer (e.g., Teric
PE64), an alkoxylated nonylphenol (e.g., Teric N10), an alkoxylated alcohol
(e.g., Teric BL8), an alkyl polyglucoside (e.g., Croda AL-2575), an
ethoxylate-propoxylate copolymer, a C10-16 alkylbenzenesulphonate
(branched or linear in solvent), a branched alcohol ether sulphate, a tallowamine alkoxylated salt, and a mineral oil (e.g., Rhodoline DF5888).
In particular embodiments, the surfactant is selected from the group
consisting of a polyoxyalkylene ether (e.g., Termul 203), an
alkylbenzenesulphonate (e.g., Ninate 60E, NANSA EVM70/2E, Kemmat
HF60), an alkoxylated styryl phenol (e.g., alkoxylated monostyryl phenols,
alkoxylated tristyryl phenols (e.g., Termul 3150), an alkoxylated oil, such as
an alkoxylated vegetable oil (e.g., Termul 1284 and Termul 1285), a
polysorbate (e.g., Tween 20) and any combination thereof.
In particular embodiments, the ratio by weight of the total amount of
solvent to the total amount of surfactant may be between about 20:1 and
about 1:1, or between about 15:1 and about 3:1, or between about 10:1 and
about 5:1 or any range therein, or it may be about 20:1, 19:1, 18:1, 17:1,
16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4.9:1, 4.8:1,
4.7:1, 4.6:1, 4.5:1, 4.4:1, 4.3:1, 4.2:1, 4.1:1, 4:1, 3.9:1, 3.8:1, 3.7:1, 3.6:1,
3.5:1, 3.4:1, 3.3:1. 3.2:1, 3.1:1. 3:1, 2:1, 1:1 or any range therein. In
particular embodiments, the ratio of solvent to surfactant may be between
about 8:1 and about 18:1.
It will be apparent in light of the foregoing that one or more
surfactants may be introduced into the formulation of the invention as a
soluble concentration in a further solvent (e.g., calcium dodecylbenzene
sulfonate in ethyl hexanol) and the latter may equate, for example, to
amounts up to about 10 g/L to about 25 g/L or more of the formulation. Given
the above, it will be appreciated that such amounts of the further solvent
may make little or no contribution to the solvency of active ingredients within the formulation of the invention.
One or more additional auxiliary agents, such as adjuvants,
preservatives, colouring agents (e.g., dyes), odourants, embittering agents
and other deterrents and the like, as are known in the art, can also be added
where desired to modify the properties of the pesticide formulation, including
the emulsifiable concentrate formulation, emulsion-in-water concentrate
formulation and the ULV liquid formulation as required.
It will be understood that it is desirable for liquid forms of the pesticide
formulation, including the emulsifiable concentrate, emulsion-in-water or
ULV liquid formulations provided herein, to be readily or easily pumped or
poured from a storage vessel. Preferably, the liquid pesticide formulation
has a viscosity at room temperature (i.e., 20 0C) of no more than 2000 cPs
(e.g., 1, 5, 10, 20, 30, 40, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900,
1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 cPs
and any range therein), as viscosities above this typically make it difficult or
impractical to pump or pour the formulation. Preferably, the liquid pesticide
formulation of the invention has a viscosity at room temperature of about or
less than 400 cPs.
With respect to the aforementioned aspect of preparing pesticide
formulations comprising a combination of spinosad and s-methoprene, it will
be appreciated that this method may be performed using methods and
commercially available equipment, such as formulation vessels and the like,
known in the art.
In a further aspect, the invention resides in a method of preventing and/or controlling a pest infestation in a storage area, comprising: mixing the pesticide formulation described above with water or a water-containing liquid to obtain a pesticide composition, and applying the pesticide composition to a material for storage in the storage area to thereby prevent and/or control the pest infestation. The material for storage may be selected from the group consisting of grain, fruit, vegetables and timber.
Suitably, the method of this aspect includes the initial step of mixing
the pesticide formulation or the emulsifiable concentrate, emulsion-in-water
or ULV liquid formulation with water or the water-containing liquid.
The terms "treat", "treating" and "treatment" are broadly intended to
include preventing or controlling a pest infestation. Treating the pest
infestation preferably results in at least maintaining, more preferably
maintaining or reducing, and even more preferably reducing the degree or
severity of the pest infestation in a target area. In one embodiment,
treatment with the pesticide formulation or the emulsifiable concentrate,
emulsion-in-water or ULV liquid formulation provided herein is able to
substantially eradicate an existing pest infestation.
As used herein, "preventing" (or "prevent" or "prevention") refers to a
course of action (such as administering an effective amount of the pesticide
formulation or the emulsifiable concentrate, emulsion-in-water or ULV liquid
formulations described herein) initiated prior to the onset of a symptom,
aspect, or characteristic of the pest infestation (e.g., plant or crop damage,
including stored crops or timber, or animal irritation) so as to prevent, reduce
or delay the symptom, aspect, or characteristic thereof. It is to be understood that such preventing need not be absolute to be beneficial to a plant, crop, animal, stored material or the like.
As generally used herein, "control" (or "controlled" or "controlling")
refers to an intervention with the pesticide formulation that reduces or
ameliorates a symptom, aspect, or characteristic of the pest infestation after
it has begun to develop. The term "ameliorating", with reference to a pest
infestation, refers to any observable beneficial effect thereto as a result of
the administration of the pesticide formulation or the emulsifiable
concentrate, emulsion-in-water or ULV liquid formulation. The beneficial
effect can be determined using any methods or standards known to the
ordinarily skilled artisan. Accordingly, these terms are meant to include any
lethal (i.e., pesticidal) or inhibitory (i.e., pestistatic) activities of the pesticide
formulation or the emulsion-in-water concentrate formulation against a
given pest, including those hereinafter described.
Herein, the terms "target area", "locus" or "space" refer to any area,
location or habitat where the prevention, control and/or eradication of a pest
infestation is needed or expected to be needed. A "target area" may include
a "storage area".
As used herein, the terms "effective amount", "pesticidally effective
amount" and "insecticidally effective amount" refer to an amount of the
pesticide formulation or the emulsifiable concentrate formulation or ULV
liquid formulation that is effective to cause such prevention, control, and/or
eradication of the pest infestation. By way of example, an effective amount
means an amount necessary to produce an observable pesticidal and/or pestistatic effect on unwanted pests (e.g., insects), including the effects of death, growth inhibition, reproduction inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of these unwanted pests. An effective amount of the pesticide formulation of the invention may vary according to the prevailing conditions such as desired pesticidal and/or pestistatic effect and duration, weather, target species, habitat, mode of application, and the like.
In particular embodiments, an effective amount is the amount of the
pesticide formulation or the emulsifiable concentrate, emulsion-in-water or
ULV liquid formulation of the invention that has an adverse effect (e.g.,
reproduction inhibition, knockdown and/or death) on at least 25% (e.g.,
25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%,
90%, 95%, 100% or any range therein) of the pests treated or contacted
therewith, more preferably at least 50% of the pests treated or contacted
therewith, and even more preferably at least 70% or greater of the pests
treated or contacted therewith.
The efficacy of the pesticide formulation of the present invention may
be monitored by determining the mortality of or adverse effect upon treated
pests (e.g., insects). This includes inhibition or modulation of pest growth,
inhibition of pest reproduction by slowing or arresting its proliferation, or
complete destruction/death of the pest. The actual value of an effective
amount for the pesticide formulation is preferably determined by routine
screening procedures employed to evaluate pesticidal activity and efficacy,
such as those methods well known in the art.
With respect to the above, an effective amount of the pesticide
formulation described herein is preferably administered to the target area or
locus of the pest infestation. By way of example, to prevent or control pest
related damage to grain in storage, an effective amount of a pesticide
formulation - comprising spinosad and s-methoprene is administered to the
storage area, or to the grain before or during storage in the storage area.
As such, a pest, and in particular insects, can be readily contacted with an
effective amount of the pesticide formulation or the emulsifiable
concentrate, emulsion-in-water or ULV liquid formulation of the invention.
The pest infestation to be prevented and/or controlled by the method
of the present aspect may be in respect of any pest, and more particularly
any insect or insects, as are well known in the art. Nonlimiting examples of
pests, and in particular insects, that may be treated by application of the
pesticide formulation of the invention include grasshoppers, locusts,
earwigs, crickets, millipedes, slaters, ants, aphids, flies, mites, ticks,
beetles, bugs, moths, springtails, caterpillars, loopers, bruchids, fleas,
mealybugs, midges, thrips, weevils, termites, butterflies and cockroaches,
which can cause significant damage to, for example, a wide range of
agricultural and horticultural crops, plants, animals and products.
In specific embodiments, the pest or pest infestation to be targeted,
prevented and/or controlled by the method for the present aspect include,
for example, Lepidoptera, Diptera, Thysanoptera, Coleoptera, Isoptera,
Homoptera, Siphonaptera, Muscidae, Anopheles, Noctuidae, Heteroptera,
Blattodea, Culicidae, Acrididae, Tabanidae and Ixodidae spp. These pests can attack a wide variety of horticultural crops, including citrus (for example, lemon, orange, grapefruit and the like), cotton, grapes, maize, canola and soya beans; harvested and stored horticultural products such as cereals, grains and timber; and agricultural animals, such as cattle, sheep and pigs.
In a particular embodiment, the pesticide formulation or the emulsifiable
concentrate, emulsion-in-water or ULV liquid formulation of the invention are
to be applied to stored grain in order to target, prevent and/or control grain
storage pests, including Saw-toothed Grain beetle (Oryzaephilus
surinamensis), Flat Grain Beetles (Cryptolestes spp.), Lesser Grain Borer
(Rhyzopertha dominica), Tropical Warehouse Moth (Ephestia cautella),
Rust-red Flour Beetle (Tribolium castaneum), Confused Four Beetle
(Tribolium confusum) Rice Weevil (Sitophilus oryzae), Granary Weevil
(Sitophilus granarius), Maize Weevil (Sitophilus zeamais) and Psocids
(Liposcelis spp.).
The pesticide formulation of the invention may be applied to the
target crop, plant, product or animal of interest, to a part thereof (such as
the leaf or seed, stored grain or timber, or animal skin), or to surroundings
thereof. Methods and techniques for applying the pesticide formulation are
known in the art and may include, for example, ground or aerial spraying
after dilution in water or a water-containing liquid.
The pesticide formulation of the invention may be applied to
harvested grain before storage, in order to obtain treated grain to be stored.
Methods and techniques for applying the emulsifiable concentrate formulation, emulsion-in-water or ULV liquid are known in the art and may include, for example, spraying.
In one embodiment, liquid forms of the pesticide formulation,
including the emulsifiable concentrate, emulsion-in-water or ULV liquid
formulation, are applied at a rate of about 1 mL to about 10 mL per tonne of
grain, e.g., about 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 mL. In some embodiments,
the about 1 mL to about 10 mL of the emulsifiable concentrate, emulsion
in-water or ULV liquid formulation is diluted in water or a water-containing
liquid to produce a pesticide formulation before application to about one
tonne of grain. The total volume of the pesticide formulation for application
to about one tonne of grain may be between about 500 mL and 2 L, e.g.,
about 500 mL, 550 mL, 600 mL, 650 mL, 700 mL, 750 mL, 800 mL, 850 mL,
900 mL, 950 mL, 1000 mL, 1050 mL, 1100 mL, 1150 mL, 1200 mL, 1250
mL, 1300 mL, 1350 mL, 1400 mL, 1450 mL, 1500 mL, 1550 mL, 1600 mL,
1650 mL, 1700 mL, 1750 mL, 1800 mL, 1850 mL, 1900 mL, 1950 mL or
2000 mL. In one particular embodiment, about 5mL of the emulsifiable
concentrate formulation is diluted to 1L in water or a water-containing liquid
per tonne of grain to be treated.
Throughout the specification the aim has been to describe the
preferred embodiments of the invention without limiting the invention to any
one embodiment or specific collection of features. It will therefore be
appreciated by those of skill in the art that, in light of the instant disclosure,
various modifications and changes can be made in the particular embodiments exemplified without departing from the scope of the present invention.
With respect to the terms "comprising", "consisting of', and
"consisting essentially of", where one of these three terms is used herein,
the presently disclosed and claimed subject matter may include the use of
either of the other two terms. Thus, in some embodiments not otherwise
explicitly recited, any instance of "comprising" may be replaced by
"consisting of' or, alternatively, by "consisting essentially of".
In the foregoing paragraphs, various ratios of components have been
disclosed. It will be appreciated that the following ratios of components can
be combined in any disclosed combination, namely:
• the ratio of active ingredients (i.e., weight of spinosad to weight of s
methoprene) may be between about 5:1 and about 1:5 or any range
therein, and
• the ratio of the first solvent to the second solvent (when present) may
be between about 1:1 and about 1:20 or any range therein, and
• the ratio of the total anionic surfactant to total non-ionic surfactant
may be between about 10:1 and about 1:10 or any range therein, and
• the ratio by weight of the total amount of solvent to the total amount
of surfactant may be between about 20:1 and about 1:1 or any range
therein.
Any reference to publications cited in this specification is not an
admission that the disclosures constitute common general knowledge in
Australia.
In order that the invention may be more readily understood and put
into practice, one or more preferred embodiments thereof will now be
described, by way of example only.
Example 1: Embodiments of Emulsifiable Concentrate
Formulations Comprising Spinosad and s-Methoprene
A number of embodiments of emulsifiable concentrate formulations across
a range of spinosad and s-methoprene concentrations and proportions, and
a range of solvents and surfactants are provided below.
Embodiment 1 - Recipe for an emulsifiable concentrate combining 100g/L
spinosad and 100g/L s-methoprene. The concentrate is produced as
below in Table 1 and, as shown in Table 2, has been determined via
assay as having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion properties upon dilution in
water prior to application; and 3) physical and chemical stability at the
point of manufacturing and again after accelerated aging to approximately
two years of shelf life.
Composition of embodiment 1 is as follows in Table 1:
Table 1:
Ingredient Role Concentration Spinosad (A, D) Active 118.5g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.7g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 108.0g/L (CAS# 65733-16-6, Technical ingredient (yields 106.1g/L s material, 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium Surfactant 44.8g/L salt in 2-ethylhexanol (CAS# 68584 23-6 in 104-76-7, e.g. Ninate 60E) Sorbitan monolaurate, polyethanoxy Surfactant 48.1g/L (20) (CAS# 9005-64-5, e.g. Tween 20) Methyl salicylate Solvent 807.9g/L (CAS# 119-36-8) (to 1127g/L total)
Chemical and physical parameters of embodiment 1 is as follows in Table
2:
Table 2:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 103.1g/L 100.0g/L Require 90.0g/L spinosad 100.0g/L Assay: 105.6g/L 106.9g/L Require 90.0g/L s-methoprene 100.0g/L pH1% 8.3 7.8 Nominally: 5.5 to 9.5 Persistent foaming 12mL 5mL Require: 60mL foam after 1 min Emulsion characteristics 0.5mL of cream; Traces of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re-emulsifies/24h Re-emulsifies/24h complete re-emulsion after 24h
Embodiment 2 - Recipe for an emulsifiable concentrate combining 100
g/L spinosad and 100 g/L s-methoprene. The concentrate is produced as below in Table 3 and, as shown in Table 4, has been determined via assay as having: 1) adequate active ingredient concentration, even after accelerated aging; 2) acceptable emulsion and dispersion properties upon dilution in water prior to application; and 3) physical and chemical stability at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.
Composition of embodiment 2 is as follows in Table 3:
Table 3:
Ingredient Role Concentration Spinosad (A, D) Active 117.8g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.1g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 108.9g/L (CAS# 65733-16-6, Technical material, ingredient (yields 107.0g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt in Surfactant 24.2g/L 2-ethylhexanol (CAS# 68584-23-6 in 104 76-7, e.g. Ninate 60E) Sorbitan monolaurate, polyethanoxy (20) Surfactant 36.8g/L (CAS# 9005-64-5, e.g. Tween 20) Methyl salicylate Solvent 846.7g/L (CAS# 119-36-8) (to 1134g/L total)
Chemical and physical parameters of embodiment 2 is as follows in Table
4:
Table 4:
Test As Accelerated Aged manufactured Result Presentation: Brown liquid Brown liquid Assay: 102.5g/L 102.2g/L Require 90.Og/L spinosad 100.0g/L Assay: 105.8g/L 105.4g/L Require 90.Og/L s-methoprene 100.0g/L pH1% 7.9 7.9 Nominally: 5.5 to 9.5 Persistent foaming 8mL 7mL Require: 60mL foam after 1 min Emulsion characteristics No cream; 1mL of cream; Require: 2mL cream after 30 min, No oil; No oil; ;trace of oil after 30 min and complete Re- Re-emulsifies/24h re-emulsion after 24h emulsifies/24h
Embodiment 3 - Recipe for an emulsifiable concentrate combining 1OOg/L
spinosad and 1OOg/L s-methoprene. The concentrate is produced as
below in Table 5 and, as shown in Table 6, has been determined via
assay as having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 3 is as follows in Table 5:
Table 5:
Ingredient Role Concentration Spinosad (A, D) Active 118.Og/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.3g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 109.Og/L (CAS# 65733-16-6, Technical material, ingredient (yields 107.1g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt Surfactant 30.3g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.4g/L (CAS# 61791-12-6, e.g. Termul 1284) Methyl salicylate Solvent 843.3g/L (CAS# 119-36-8) (to 1131g/L total)
Chemical and physical parameters of embodiment 3 is as follows in Table
6:
Table 6:
Test As Accelerated manufactured Aged Result Presentation: Brown liquid Brown liquid Assay: 102.4g/L 100.1g/L Require 90.0g/L spinosad 100.0g/L Assay: 105.9g/L 105.3g/L Require 90.0g/L s-methoprene 100.0g/L pH1% 8.1 8.1 Nominally: 5.5 to 9.5 Persistent foaming 12mL 8mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; ;trace of oil after 30 min and complete Re- Re re-emulsion after 24h emulsifies/24h emulsifies/24h
Embodiment 4 - Recipe for an emulsifiable concentrate combining 1OOg/L
spinosad and 1OOg/L s-methoprene. The concentrate is produced as
below in Table 7 and, as shown in Table 8, has been determined via assay as having: 1) adequate active ingredient concentration, even after accelerated aging; 2) acceptable emulsion and dispersion properties upon dilution in water prior to application; and 3) physical and chemical stability at the point of manufacturing and again after accelerated aging to approximate two years of shelf life.
Composition of embodiment 4 is as follows in Table 7:
Table 7:
Ingredient Role Concentration Spinosad (A, D) Active 118.3g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.6g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 109.4g/L (CAS# 65733-16-6, Technical material, ingredient (yields 107.5g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium Surfactant 30.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.5g/L (CAS# 61791-12-6, e.g. Termul 1284) Oil of wintergreen Solvent 842.0g/L (CAS# 68917-75-9) (to 1130g/L total)
Chemical and physical parameters of embodiment 4 is as follows in Table
8:
Table 8:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 107.0g/L 104.1g/L Require 90.0g/L ! spinosad 100.0g/L Assay: 105.7g/L 105.5g/L Require 90.0g/L s-methoprene 100.0g/L pH1% 7.7 8.4 Nominally: 5.5 to 9.5 Persistent foaming 9mL 2mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h
Embodiment 5 - Recipe for an emulsifiable concentrate combining 100g/L
spinosad and 100g/L s-methoprene. The concentrate is produced as
below in Table 9 and, as shown in Table 10, has been determined as
having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 5 is as follows in Table 9:
Table 9:
Ingredient Role Concentration Spinosad (A, D) Active 118.4g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.6g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 109.0g/L (CAS# 65733-16-6, Technical ingredient (yields 107.1g/L s material, 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium Surfactant 31.1g/L salt in 2-ethylhexanol (CAS# 68584 23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.2g/L (CAS# 61791-12-6, e.g. Termul 1284) Alkyl polyoxyalkylene ether Surfactant 10.2g/L (CAS# Proprietary, e.g. Termul 203) Methyl salicylate Solvent 831.8g/L (CAS# 119-36-8) (to 1131g/L total)
Chemical and physical parameters of embodiment 5 is as follows in Table
10:
Table 10:
Test As Accelerated manufactured Aged Result Presentation: Brown liquid Brown liquid Assay: 105.4g/L 101.7g/L Require 90.0g/L spinosad 100.0g/L Assay: 105.6g/L 105.7g/L Require 90.0g/L s-methoprene 100.0g/L pH1% 7.7 8.1 Nominally: 5.5 to 9.5 Persistent foaming 7mL 5mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Traces of cream; Require: 2mL cream after 30 min, !trace No oil; No oil; of oil after 30 min and complete re- Re- Re emulsion after 24h emulsifies/24h emulsifies/24h
Embodiment 6 - Recipe for an emulsifiable concentrate combining 1OOg/L
spinosad and 1OOg/L s-methoprene. The concentrate is produced as
below in Table 11 and, as shown in Table 12, has been determined via
assay as having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 6 is as follows in Table 11:
Table 11:
Ingredient Role Concentration Spinosad (A, D) Active 118.3g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.6g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 109.1g/L (CAS# 65733-16-6, Technical material, ingredient (yields 107.2g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt Surfactant 18.8g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Ethoxylated tristyrylphenol Surfactant 43.1g/L (CAS# 99734-09-5, e.g. Termul 3150) Methyl salicylate Solvent 846.Og/L (CAS# 119-36-8) (to 1135g/L total)
Chemical and physical parameters of embodiment 6 is as follows in Table
12:
Table 12:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 104.2g/L 100.3g/L Require 90.Og/L:5 spinosad 100.0g/L Assay: 105.5g/L 105.8g/L Require 90.Og/L: s-methoprene 5 100.0g/L pH1% 7.9 8.1 Nominally: 5.5 to 9.5 Persistent foaming 7mL 8mL Require: 60mL foam after 1 min Emulsion characteristics No cream; Traces of cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h
Embodiment 7 - Recipe for an emulsifiable concentrate combining 1OOg/L
spinosad and 100g/L s-methoprene. The concentrate is produced as
below in Table 13 and, as shown in Table 14, has been determined via
assay as having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 7 is as follows in Table 13:
Table 13:
Ingredient Role Concentration Spinosad (A, D) Active 118.Og/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 100.3g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 109.1g/L (CAS# 65733-16-6, Technical material, ingredient (yields 107.2g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt Surfactant 30.6g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.6g/L (CAS# 61791-12-6, e.g. Termul 1284) N-methyl pyrrolidone (CAS# 872-50-4) Solvent 400.1g/L Methyl salicylate Solvent 389.4g/L (CAS# 119-36-8) (to 1078g/L total)
Chemical and physical parameters of embodiment 7 is as follows in Table
14:
Table 14:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 100.6g/L 97.2g/L Require 90.0g/L spinosad 100.0g/L Assay: 104.4g/L 104.4g/L Require 90.0g/L:5 s-methoprene 5 100.0g/L pH1% 8.0 8.3 Nominally: 5.5 to 9.5 Persistent foaming 9mL 4mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h
Embodiment 8 - Recipe for an emulsifiable concentrate combining 50g/L
spinosad and 50g/L s-methoprene. The concentrate is produced as below
in Table 15 and, as shown in Table 16, has been determined via assay as
having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 8 is as follows in Table 15:
Table 15:
Ingredient Role Concentration Spinosad (A, D) Active 59.2g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 50.3g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 54.9g/L (CAS# 65733-16-6, Technical material, ingredient (yields 54.Og/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt Surfactant 30.3g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.5g/L (CAS# 61791-12-6, e.g. Termul 1284) Methyl salicylate Solvent 977.Og/L (CAS# 119-36-8) (to 1152g/L total)
Chemical and physical parameters of embodiment 8 is as follows in Table
16:
Table 16:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 54.8g/L 50.1g/L Require 45.0g/L ! spinosad 55.0g/L Assay: 54.2g/L 52.7g/L Require 45.0g/L s-methoprene 55.0g/L pH1% 7.5 8.3 Nominally: 5.5 to 9.5 Persistent foaming 11mL 9mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; <trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h
Embodiment 9 - Recipe for an emulsifiable concentrate combining 10g/L
spinosad and 10g/L s-methoprene. The concentrate is produced as below
in Table 17 and, as shown in Table 18, has been determined via assay as
having: 1) adequate active ingredient concentration, even after
accelerated aging; 2) acceptable emulsion and dispersion properties upon
dilution in water prior to application; and 3) physical and chemical stability
at the point of manufacturing and again after accelerated aging to
approximate two years of shelf life.
Composition of embodiment 9 is as follows in Table 17:
Table 17:
Ingredient Role Concentration Spinosad (A, D) Active 11.8g/L (CAS# 131929-60-7, 131929-63-0, ingredient (yields 10.0g/L Technical material, 85.0%) insecticide spinosad) s-Methoprene Active 11.Og/L (CAS# 65733-16-6, Technical material, ingredient (yields 10.8g/L s 98.3%) insecticide methoprene) Alkylbenzenesulfonic acid, calcium salt Surfactant 30.0g/L in 2-ethylhexanol (CAS# 68584-23-6 in 104-76-7, e.g. Ninate 60E) Castor oil ethoxylate Surfactant 30.0g/L (CAS# 61791-12-6, e.g. Termul 1284) Oil of wintergreen Solvent 1081.9g/L (CAS# 68917-75-9) (to 1165g/L total)
Chemical and physical parameters of embodiment 9 is as follows in Table
18:
Table 18:
Test As manufactured Accelerated Aged Result Presentation: Brown liquid Brown liquid Assay: 10.5g/L 10.0g/L Require 8.5g/L spinosad 10.5g/L Assay: 10.8g/L 10.8g/L Require 8.5g/L s-methoprene< 10.50g/L pH1% 7.6 8.1 Nominally: 5.5 to 9.5 Persistent foaming 9mL 9mL Require: 60mL foam after 1 min Emulsion characteristics No cream; No cream; Require: 2mL cream after 30 min, No oil; No oil; trace of oil after 30 min and Re- Re-emulsifies/24h complete re-emulsion after 24h emulsifies/24h
Example 2: Spinosad 100g/L + s-Methoprene 100 g/L EC Raw Material
Identities
An example formulation combining 100g/L spinosad and 100g/L s
methoprene is provided below in Table 19, which includes the purity (where
known), source and technical details of the components. The spinosad
technical and s-methoprene technical are the same as that used in the
formulations of Example 1.
Co C) m 00
.0.
o: CD CD~ ~ U 0 )
0 3 ,C.)') c 4 <
M 1 :3 U cy a) T-~ LC 0 * M ) UCC E- CD 00 -o r
-N~ ~" -,,eL c
cU) E >N m " c"o >% m < ED o () > Lo LO Q c =C)- OV E C -6 V 2 0 a) WO) CD 64Ci w - 1 C)-v (1 >(l CL(0 co ) EU)- U
m )U M CUo Z Q-U 7E* ~ ) ~ i.. O EC N. ) C C~oc 21 U 2
o U) E EO DO E 53
-0 :3 Lt) cu >, C) >,- x0 .04~
m 0 0 =~ 0. 3U) a U)cZe: CL ml 0!E2)" 4U U)
w 0 002
-CC.T - __ _u __ _ua)___
Example 3: Method of Manufacture of Spinosad and s-Methoprene
Emulsifiable Concentrate Formulation
Formulation of a 10,OOOL batch of product, inclusive of quality control
measures, is as follows:
Formulation Procedure
1. Ensure formulation vessel is empty and clean
2. Charge solvent component(s), holding a small proportion back (e.g. -5%)
for subsequent addition, to the formulation vessel with the agitator
operating
3. Charge active ingredients (spinosad and s-methoprene) to the formulation
vessel with continuous agitation
4. Charge the surfactant(s) and other excipients clearing residual
components from any pumps or process lines used with the remaining
complement of solvent
5. Continue agitating for a minimum of 30 minutes following the last
ingredient's addition
Quality Control Procedure
1. Sample approximately 1L of product, ensuring it is representative
2. Sub-sample 250mL from the original 1L sample, and subject it to the
following testing regime.
2.1. Specific gravity (CIPAC MT3.1)
If specific gravity is within the bounds of the acceptable range listed in the
specification, record the value and proceed to the next test. If specific
gravity is outside of the bounds of the acceptable range listed in the specification, agitate the formulation charge until specific gravity is constant. If still outside of the bounds of the acceptable range, quarantine batch for further investigations and possible rework.
2.2. pH 1% aqueous (CIPAC MT75.3)
If pH 1% aqueous is satifactory, record results and proceed to the next
test. If pH 1% aqueous is outside the bounds of the acceptable range
listed in the specification, quarantine the batch for further investigations
and possible rework.
2.3. Emulsion characteristics (CIPAC MT36.1)
If emulsion stability in standard hard water is satifactory, record results and
proceed to the next test. If emulsion stability is outside the bounds of the
acceptable range listed in the specification, adjust the contents of
surfactants. After suitable agitation time to ensure homogeneity, resample
and retest. Repeat adjustment process until emulsion stability is within
the bounds of the acceptable range.
2.4. Persistent foam (CIPACMT47.2)
If persistent foaming characteristics are satifactory, record results and
proceed to the next test. If persistent foaming characteristics are outside
the bounds of the acceptable range quarantine the batch for further
investigations and possible rework.
2.5. Active constituent (spinosad or s-methoprene) content
(appropriately validated method). If active constituent level is satifactory,
record results. If active constituent level is outside the bounds of the
acceptable range listed in the specification, adjust the level accordingly by adding additional solvent and/or surfactants and/or other excipients (for a high active constituent content), or additional technical active constituent spinosad and/or s-methoprene (for a low active content). After suitable agitation time to ensure homogeneity, resample and retest. Repeat adjustment process until active constituent levels are within the bounds of the acceptable range.
3. Catalogue and store a retention sample of approximately 200g
4. Generate a certificate of analysis noting results of testing
5. Issue quality clearance giving authority to package goods
6. Package the finished goods ensuring both the batch number and
manufacturing date is noted on the label.
Example 4: Bio-efficacy of Emulsifiable Concentrate Formulations
Comprising Spinosad and s-Methoprene
Trials have been carried out to compare the activity and efficacy of an
emulsifiable concentrate formulation of the present invention with a currently
available product for controlling an infestation of Rust Red Flour Beetle
(Tribolium castaneum) or the Lesser Grain Borer (Rhyzoperth dominica).
A. Rust Red Flour Beetle
In this trial, a formulation of Embodiment 3 (as described above) was
compared to Conserve Plus Grain Protector (APVMA No. 81465; Dow
AgriSciences Australia Pty Ltd; batch no. C781H9DOOO). Both concentrate
formulations were diluted in water at the amounts of 0.5, 1 and 2 mL per litre of
water to form pesticide compositions for application. Clean wheat samples were then treated with aliquots of these pesticide compositions and then, 1 day after treatment (DAT), infested with 20 individual Rust Red Flour Beetles to simulate a natural incursion. Each of the sealed microcosms (simulating a sealed silo) containing treated wheat and 20 individual beetles were then analysed after 4 and 8 days after incorporation (DAI) for mortality. Results of these trials are provided below in Table 14, which shows the mean number of dead beetles per microcosm and the % corrected mortality using Abbott's Formula (Mortality % =
(1-Tn after treatment/ Cn after treatment) * 100, where Tn = number of live
insects in treatment and Cn= number of live insects in control).
Table 14
No. Formulation and 4 DAI 4 DAI 8 DAI 8 DAI Application % Corrected % Corrected Rate Mortality Mortality 1 Untreated - 2.8 - 7.5 0 g.ai/t grain 2 Conserve Plus- 2.8 0.3 20.0 100.0 0.05 g.ai/t grain 3 Embodiment 3- 8.0 30.2 20.0 100.0 0.05 g.ai/t grain 4 Conserve Plus - 9.0 35.6 20.0 100.0 0.10 g.ai/t grain 5 Embodiment 3 - 17.8 87.2 20.0 100.0 0.10 g.ai/t grain 6 Conserve Plus - 13.3 60.9 20.0 100.0 0.20 g.ai/t grain 7 Embodiment 3 - 17.3 84.0 20.0 100.0 0.02 g.ai/t grain P value <0.001 <0.001 <0.001 1 LSD 11.09 8.34 1.67 ns The treatment analysis in Table 14 clearly shows that, except for Conserve Plus
at 0.05 gram active / Tonne, all treatments provided significant control of Rust
Red Flour Beetles when compared to the Untreated control throughout the
duration of the trial. However, significant differences were exhibited between
treatments at the first assessment (4 DAI), where Embodiment 3 was
significantly superior in controlling Rust Red Flour Beetle. This shows that the
formulations of the present invention show a faster initial activity after infestation
of a wheat silo by Rust Red Flour Beetle, compared to the currently available
Conserve Plus product.
B. Lesser Grain Borer
The above comparative trial was also completed with the Lesser Grain
Borer as the invasive pest species. The only difference in experimental design
was the incorporation of the 20 individual borers 5 days after treatment. The
results are shown below in Table 15.
Table 15:
No. Formulation and Application Rate 4 DAI 4 DAI % Corrected Mortality 1 Untreated - 1.3 0 g.ai/t grain 2 Conserve Plus - 0.05 g.ai/t grain 19.5 97.1 3 Embodiment 3 - 0.05 g.ai/t grain 20.0 100.0 4 Conserve Plus - 0.10 g.ai/t grain 20.0 100.0 5 Embodiment 3 - 0.10 g.ai/t grain 20.0 100.0 6 Conserve Plus - 0.20 g.ai/t grain 20.0 100.0 7 Embodiment 3 - 0.02 g.ai/t grain 20.0 100.0 P value <0.001 0.445 LSD 11.09 ns
As seen in Table 15, all treatments provided significant control over Lesser
Grain Borers when compared to the Untreated control. Accordingly, formulations of the present invention are as effective as the Conserve Plus product in the initial treatment of an infestation of the Lesser Grain Borer.
Claims (5)
1. A pesticide formulation comprising:
spinosad;
s-methoprene;
a surfactant; and
a solvent,
wherein the formulation is an emulsifiable concentrate, an emulsion or
an ultra low volume (ULV) liquid.
2. The pesticide formulation of claim 1, wherein:
the spinosad is present at a concentration of at least about 5 g/L, or
between about 10 g/L and about 150 g/L, of the total weight of the formulation;
the s-methoprene is present at a concentration of at least about 5 g/L, or
between about 5g/L and about 150 g/L, of the total weight of the formulation;
the surfactant is selected from a non-ionic surfactant, an anionic
surfactant or a mixture thereof, and is present in an amount of at least 50 g/L,
or between about 50g/L and about 150 g/L; and
wherein the solvent comprises methyl salicylate in an amount of at least
650 g/L of the total volume of the formulation, and
wherein the formulation is an emulsifiable concentrate.
3. A pesticide formulation, comprising:
spinosad at a concentration of at least about 100 g/L;
s-methoprene at a concentration of at least about 100 g/L; a non-ionic surfactant comprising a polyoxyethylenesorbitan monolaurate; an anionic surfactant comprising a calcium salt of an alkylbenzene sulfonate, wherein the ratio of non-ionic surfactant to anionic surfactant is 1:1; and a solvent comprising methyl salicylate, wherein the formulation is an emulsifiable concentrate.
4. A method of producing a pesticide formulation of any one of claims 1 to
3, comprising the steps of (a) combining the spinosad, s-methoprene, a
surfactant and a solvent, and (b) mixing to form a pesticide formulation.
5. A method of preventing and/or controlling a pest infestation in a storage
area, comprising:
mixing the pesticide formulation of any one of claims 1 to 3 with water or
a water-containing liquid to obtain a pesticide composition, and
applying the pesticide composition to a material for storage in the storage
area to thereby prevent and/or control the pest infestation,
wherein the material for storage is selected from the group consisting of
grain, fruit, vegetables and timber.
Imtrade Australia Pty Ltd Patent Attorneys for the Applicant/Nominated Person
SPRUSON&FERGUSON
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