NZ730867B2 - Pesticide formulations having physical mode of action - Google Patents
Pesticide formulations having physical mode of action Download PDFInfo
- Publication number
- NZ730867B2 NZ730867B2 NZ730867A NZ73086715A NZ730867B2 NZ 730867 B2 NZ730867 B2 NZ 730867B2 NZ 730867 A NZ730867 A NZ 730867A NZ 73086715 A NZ73086715 A NZ 73086715A NZ 730867 B2 NZ730867 B2 NZ 730867B2
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- New Zealand
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- sol
- pest
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- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
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Classifications
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- A—HUMAN NECESSITIES
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- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- 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
- A01N25/26—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 in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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- A—HUMAN NECESSITIES
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- 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
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- 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
- A01N43/14—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 six-membered rings
- A01N43/16—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 six-membered rings with oxygen as the ring hetero atom
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- 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
- A01N43/24—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 two or more hetero atoms
- A01N43/26—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 two or more hetero atoms five-membered rings
- A01N43/28—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 two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
- A01N43/30—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 two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
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- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
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- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- 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
Abstract
The invention relates to pesticidal compositions comprising trisiloxane surfactants and a matrix-forming agent, which compositions are capable of controlling pests and pathogens using a physical mode of action. Accordingly, in one aspect, the present disclosure provides a pesticidal composition for controlling pests and pathogens with a physical mode of action. The composition comprises trisiloxane surfactants and matrix-forming agents. The composition may form a gel matrix or a film matrix. The trisiloxane surfactants may be selected from the group consisting of Silwet L-77, Silwet 408, Break-Thru S-240, and Silibase 2848. The matrixforming agents of a pesticidal composition are selected from the group consisting of chitosan salts and sol-gel precursors.
Description
PESTICIDE FORMULATIONS HAVING PHYSICAL MODE OF ACTION CROSS-REFERENCE TO RELATED ATION This application relates to and claims the priority of U.S. Provisional Patent Application Serial No. 62/063,504, which was filed October 14, 2014 and is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION The present invention relates to compositions capable of controlling pests and pathogens with a physical mode of action.
OUND OF THE INVENTION Agricultural losses are ily caused by insect pest damage and plant ens. Insects may also act as vectors of ial or viral plant pathogens where controlling the insect vector is the only means of preventing ion. Insect and pathogen induced spoilage of agricultural commodities, such as fruits and vegetables, has been estimated to result in losses of approximately 30% of crops in the United States and up to 50% of crops worldwide. Thus, ive ltural practices to control insect pests and pathogens are essential to prevent excessive crop losses.
However, using chemical pesticides on plants and animals may cause acute and chronic ty, carcinogenicity, and other negative effects on the humans and animals that come into contact with them. Humans and animals who consume produce that has been treated with or has come in contact with conventional pesticides, as well those humans and animals who are exposed to the environmental conditions the pesticides leave behind, are at risk.
Additionally, strains of pesticide resistant insects are increasing at alarming rates, rendering chemical treatments less, or even completely ineffective for agricultural purposes.
Accordingly, there is a need in the art for new methods of controlling pests, ing insects that destroy agricultural commodities and infest animals, which methods are effective, safer to humans, and environmentally benign.
SUMMARY OF THE INVENTION In one aspect, the present disclosure provides a non-therapeutic use of a composition comprising a. at least one trisiloxane surfactant having Formula (I): wherein R is -(CH2)3-(OCH2CH2)nOR1; R1 is -H, -CH3, or -O(O)CCH3; and n is 2 to 20; and b. a matrix-forming agent in a form of at least one metal or metalloid alkoxide sol-gel precursor, preferably n or titanium alkoxide sol-gel sor, wherein the ation of the constituents a. and b. has pesticidal properties, for controlling and/or killing a pest or a pathogen by applying the composition to a pest, a pathogen or a locus.
In another aspect, the present disclosure provides a pesticidal composition for controlling pests and pathogens with a physical mode of action. The composition comprises trisiloxane surfactants and matrix-forming . The composition may form a gel . The trisiloxane surfactants may be selected from the group consisting of Silwet L-77, Silwet 408, Break-Thru S-240, and Silibase 2848. The matrix-forming agents of a pesticidal composition are in a form of at least one metal or metalloid alkoxide sol-gel precursor, preferably silicon or titanium de sol-gel precursor. Furthermore a idal composition does not comprise any acid or base catalyst.
When the matrix-forming agents are sol-gel precursors, the trisiloxane surfactants are present in an amount of about 95% to about 99.9% (wt/wt) and the sol-gel precursors are present in an amount of about 0.1% to about 5% (wt/wt). The sol-gel precursor may be tetraethyl orthosilicate. When the sol-gel precursor is tetraethyl orthosilicate the composition may comprise trisiloxane surfactants are present in an amount of about 99% (wt/wt), and tetraethyl orthosilicate is present in an amount of about 1% (wt/wt).
Compositions of the present disclosure may r comprise an insecticide synergist such as piperonyl butoxide. Compositions may also further se a pesticide.
In r aspect, the present disclosure provides a pesticidal composition for lling pests and pathogens with a al mode of action comprising at least one trisiloxane surfactant and at least one sol-gel precursor. The at least one trisiloxane surfactant may be t in an amount of about 95% to about 99.9% (wt/wt), and the at least one sol-gel precursor may be present in an amount of about 0.1% to about 5% (wt/wt).
A r aspect of the present disclosure provides a pesticidal composition for controlling pests and pathogens with a physical mode of action comprising about 99% (wt/wt) silibase 2848 trisiloxane surfactant and about 1% (wt/wt) tetraethyl orthosilicate matrix-forming agent.
Another aspect of the present disclosure provides a pesticidal composition for controlling pests and pathogens with a physical mode of action comprising about 90% ) se 2848 trisiloxane surfactant, about 1% (wt/wt) thyl orthosilicate matrix-forming agent, and about 10% piperonyl butoxide.
A further aspect of the present disclosure provides a method of lling a pest or a pathogen, the method comprising applying a pesticidal composition having a physical pesticidal mode of action to a pest or a locus. The composition comprises trisiloxane surfactants and matrix-forming agents.
Another aspect of the present disclosure provides a method of killing a pest, the method comprising applying a pesticidal composition having a physical pesticidal mode of action to a pest. The ition comprises trisiloxane surfactants and -forming agents.
A r aspect of the present disclosure provides a method of preparing an emulsifiable concentrate formulation of a pesticidal composition according to the present invention comprising trisiloxane surfactants and sol-gel precursors, the method comprising ing the trisiloxane surfactants and the sol-gel precursors to generate an emulsifiable concentrate.
A further aspect of the present disclosure provides a method of applying a formulation of a pesticidal composition comprising trisiloxane surfactants and matrix-forming agents, the method comprising diluting the formulation in water to generate a diluted pesticidal composition sing about 0.01 to about 4% ) trisiloxane surfactant, and applying the diluted composition to a surface.
DETAILED DESCRIPTION The present invention provides pesticidal compositions capable of controlling pests and pathogens using a physical mode of action. Compositions of the present disclosure comprise trisiloxane surfactants and matrix-forming agents, and are capable of forming a lasting matrix. It was singly discovered by the inventors that a matrix formed by compositions comprising trisiloxane surfactants can effectively l a wide variety of fungi, viruses, bacteria, mites, insects, and nematodes. ageously, compositions of the present disclosure are safe for workers, consumers, and the nment, and are effective in controlling pests and pathogens without the need for conventional pesticides having a chemical mode of action.
Methods of preparing and stering compositions of the disclosure are also described. Various aspects of the invention are described in further detail in the following sections.
I. COMPOSITIONS One aspect of the t invention es compositions comprising a trisiloxane surfactant and a matrix-forming agent. The term x" as used herein, describes any ure formed by the dispersion of a composition of the present disclosure on a surface. Non-limiting examples of a matrix formed by a composition of the present disclosure include a gel, a film, or a fiber. While not wishing to be bound by theory, it is believed that oxane surfactants and matrix-forming agents, when combined in compositions of the present disclosure and applied on a surface such as a pest, control pests using a physical mode of action by spreading y over a pest's body, infiltrating the tracheal system and forming a lasting matrix capable of effectively suffocating the pest. It is also believed that compositions of the present disclosure can form a lasting matrix on a surface such as a leaf, thereby physically protecting the leaf from further infestation by pests, or inducing resistance against fungi, viruses, and bacteria. a. oxane surfactants Surfactants (alternatively referred to as a ce acting agents" or "detergents") are nds that reduce surface tension (or interfacial tension) when dissolved in water or water solutions, or that reduce surface n between two liquids or n a liquid and a solid. For instance, in a spray composition, surfactants enhance the spreading of spray droplets on a surface such as on a leaf or on an insect.
Presently described compositions comprise a trisiloxane surfactant sing Formula (I): wherein R is -(CH2)3-(OCH2CH2)nOR1; R1 is -H, -CH3, or -O(O)CCH3; and n is 2 to 20.
Trisiloxane surfactants are especially effective at reducing the surface tension of water, thereby ng a drop of a composition comprising trisiloxane surfactants to spread to a diameter at least 9 times as great as a doubly-distilled drop of water on a hydrophobic surface such as the leaf of a plant.
Presently described compositions comprise at least one trisiloxane surfactant.
For ce, a composition may comprise 1, 2, 3, 4, 5, 6, 7, 8 9, 10 or more trisiloxane surfactants. ably, a composition comprises 1, 2, 3, or 4, trisiloxane surfactants. More preferably, a composition comprises one trisiloxane tant.
Trisiloxane surfactants are commercially available from a variety of sources.
Non-limiting examples of cially available trisiloxane surfactants suitable for use in a composition of the present disclosure include Silwet L-77® SILWET 408®, SILWET Y-12808®, SILWET L-7607®, SILWET L-7602®, SILWET L-7210®, SILWET L-7002®, SILWET L-720®, and SILWET L-7200® (all of which are registered arks of OSi lties), Break-Thru S-240® (a registered trademark of Evonik Industries), Sylgard 309® (a registered trademark of Dow Corning Corporation), and Silibase 2848. Preferred commercially available trisiloxane surfactants are Silwet L-77®, Silwet 408®, Thru , and Silibase 2848. b. Matrix-forming compositions Trisiloxane surfactants are capable of forming a lasting matrix when combined with a matrix-forming agent and applied to a surface. As used herein, the term "lasting" describes the duration of time that a composition of the present disclosure may be capable in controlling a pest or pathogen. For instance, a lasting matrix may be capable of controlling pests or pathogens for 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or days after application or longer.
The term "matrix-forming agent" as used herein, bes any agent e of reacting or interacting with itself or with a trisiloxane surfactant of the composition to form a hybrid al with altered physical properties when compared to the individual components alone. Matrix-forming agents ing to the present invention are sol-gel sors capable of forming a gel matrix in a composition comprising trisiloxanes. Compositions comprising each matrix-forming agent are described in more detail below.
A. Compositions comprising trisiloxanes and sol-gel precursors Matrix-forming agents are sol-gel precursors. The sol-gel process may be described as the polycondensation reactions of one or more siloxane molecular precursors (e.g. trisiloxane surfactants and l precursors) in a liquid leading to the formation of a 1-, 2-, or 3-dimensional k or gel matrix of siloxane bonds. As it was discovered by the inventors, trisiloxane surfactants may be capable of forming a gel matrix by the sol-gel process when combined with sol-gel precursors.
Presently described compositions may comprise a single sol-gel precursor or a mixture of sol-gel precursors. For instance, a composition may comprise 1, 2, 3, 4, , 6, 7, 8, 9, 10 or more sol-gel precursors. Preferably, a ition comprises 1, 2, 3, or 4 sol-gel precursors. More preferably, a composition comprises one l precursor.
Sol-gel precursors suitable for the purposes of the ion are known in the art. Precursors used in sol-gel processing consist of a metal or metalloid element such as silicon, boron, aluminium, titanium, zinc, and zirconium, surrounded by various reactive ligands. Preferably, a sol-gel precursor of the present disclosure is a metal alkoxide. More preferably, a metal alkoxide sol-gel precursor is a n alkoxide. When a silicon alkoxide precursor is used in a sol-gel process, a number of reactions result, including hydrolysis, which leads to the formation of silanol groups Si—OH, and condensation, which gives siloxane Si—O—Si . miting es of silicon alkoxide sol-gel precursors include H5)4 (tetraethyl orthosilicate or TEOS) or Si(OCH3)4 (tetramethyl orthosilicate or TMOS). A preferred sol-gel precursor suitable for use in a composition of the present disclosure is TEOS.
Desired physical and performance characteristics of a sol-gel matrix resulting from a composition comprising trisiloxane surfactants and sol-gel precursors can and will vary depending in part on the trisiloxane tants and sol-gel precursors used in a ition, the number of and the relative amounts of oxane tants and precursors in a composition, and the compositions, and may be determined experimentally.
Presently described compositions comprising trisiloxane surfactants and solgel precursors may be formulated as described in n II for application to a pest or pathogen or a locus of pest or pathogen. Preferably, compositions comprising trisiloxane surfactants and sol-gel precursors are formulated as an emulsifiable concentrate (EC). An EC formulation comprising trisiloxane surfactants and sol-gel precursors of the present disclosure may be prepared by combining the trisiloxane surfactants and sol-gel precursors to form an EC ation. An EC formulation of the present disclosure may comprise about 0.1, 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 85, 90, 95, or about 99% ) or more trisiloxane surfactants. Preferably, EC formulations may se about 90, 95, 96, 97, 98, 99% (wt/wt) or more trisiloxane tants. More preferred are formulations comprising about 98, 98.1, 98.2, 98.3, 98.4, 98.5, 98.6, 98.7, 98.8, 98.9, 99, 99.1, 99.1, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, or 99.9% (wt/wt) or more trisiloxane surfactants.
An EC formulation comprising trisiloxane surfactants and sol-gel precursors of the present disclosure may comprise about 0.1, 1, 2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, or about 90% (wt/wt) or more sol-gel precursors. Preferably, compositions may comprise about 0.1, 1, 2, or 5% ) l precursors. More preferred are itions comprising about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 0.7, 1.8, 1.9 or about 2% (wt/wt) sol-gel precursors.
An EC formulation may further comprise an insecticide synergist. An insecticide synergist may be as described in Section lie below. Preferably, when an EC formulation of the present disclosure further comprises an insecticide synergist, the synergist is piperonyl butoxide (PBO). An EC formulation sing trisiloxane surfactants and sol-gel precursors and further comprising about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20% (wt/wt) or more PBO, preferably about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15% (wt/wt) PBO, and more preferably about 8, 9, 10, 11, or about 12% (wt/wt) PBO.
In general, an EC formulation is diluted in water before using to control microorganisms and invertebrate pests. An EC formulation of a presently described composition may be diluted in water to generate a ation comprising about 0.01 to about 3% (wt/wt) trisiloxane surfactant, preferably 0.1 to about 1% (wt/wt) oxane surfactant, and more preferably, 0.125 to about 0.175% (wt/wt) trisiloxane tant.
II. METHOD OF USE The present disclosure provides a method of controlling pests and pathogens which comprises applying an effective amount of a composition of the present disclosure to a pest or pathogen or a locus of pest or pathogen. The term "locus of pest or pathogen" as used herein may be used to describe any surface that may be infested with a pest or pathogen, a surface susceptible to attack by a pest or pathogen, or a surface where a pest or pathogen may be found. For instance, a locus of pest or pathogen may be a leaf, the body of a mammal or bird, or a de structure. a. Control of pests and pathogens Compositions of the present disclosure may be used to control infestations of microorganisms and invertebrate pests. Preferably, compositions are used to control infestations of microorganisms. As used herein, the term "microorganisms" may be used to describe bacterial, viral and fungal microorganisms. Also preferably, compositions are used to control infestations of invertebrate pests. As used herein, the term "invertebrate pests" may be used to describe insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and other invertebrate pests such as acarine, nematode and mollusc pests.
The pests and pathogens which may be controlled by the use of the invention compositions include those pests and pathogens associated with agriculture, which term includes the growing of crops for food and fiber products. Compositions of the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens, for example rs, as well as for tree injection, pest management and the like.
Compositions of the ion may also be useful in the field of animal health, and may be used on an animal t microorganisms and parasitic invertebrate pests. Preferably, compositions of the invention are used against parasitic invertebrate pests on an animal. Examples of pests include nematodes, trematodes, cestodes, flies, mites, ticks, lice, fleas, chiggers, true bugs and maggots. The animal may be a non-human animal, e.g. an animal associated with agriculture, e.g. a cow, a pig, a sheep, a goat, a horse, or a donkey, or a companion animal, e.g. a dog or a cat. ably, tly bed compositions are used to control soft-bodied pests. Non-limiting examples of pest species which may be lled by compositions of the present sure include: Rhopalosiphum padi (aphid), Myzus persicae (aphid), Brevicoryne brassicae (aphid), Aphis gossypii (aphid), Aphis fabae ), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), ettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis ), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Meligethes aeneus (pollen beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Parthenolecanium pomeranicum (scale s), Trialeurodes spp. (white , Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), his virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), s spp. (cutworms), Chilo suppressalis (rice stem , Locusta migratoria t), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Varroa ctor a mites), Boophilus microplus (cattle tick), entor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. lies), Blattella germanica (cockroach), Periplaneta ana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the ermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. icus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulfureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. g and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) ras latum (slug), Haematobia (Lyperosia) irritans (horn fly), Dermanyssus galinae (poultry red mite), Simulium spp. (blackfly), Glossina spp. (tsetse , Hydrotaea ns (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Morellia simplex (sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia ta, Lucilia cuprina (green blowfly), hora spp. (blowfly), Stomoxys calcitrans (stable fly), Protophormia spp., Oestrus ovis (nasal botfly), Culicoides spp. (midges), Chrysops spp. (deer fly), Hippobosca equine, Gastrophilus intestinalis, Gastrophilus rhoidalis, lice such as Bovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicola subrostratus, doxus spiniger, Lignonathus setosus and Trichodectes canis, keds such as Melophagus ovinus, and mites such as tes spp., Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella spp., Notoedres cati, Trombicula spp. and Otodectes cyanotis (ear , ticks such as Argasidae spp., Argalphas spp., and Ornithodoros spp., Ixodidae spp., Rhipicephalphalus sanguineus, Dermacentor variabilis, Dermacentor andersoni, Amblyomma americanum, Ixodes scapularis and other Rhipicephalus spp. b. Formulation Compositions of the present disclosure may be formulated for application to animals or to plants. Formulation types may e dustable s (DP), soluble powders (SP), water soluble granules (SG), water sible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra-low volume liquids (UL), emulsifiable concentrates (EC), sible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), ls, g/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of a composition.
Dustable powders (DP) may be prepared by mixing a composition of the disclosure with one or more solid diluents such as natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous , calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers, and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a composition of the disclosure with one or more wetting agents, one or more dispersing agents, one or more anti-caking agents, one or more low aids, one or more water soluble , or a mixture of said agents to improve water dispersibility/solubility. The e is then ground to a fine . Similar compositions may also be granulated to form water e granules (SG) for instance, by using a roll-pressing granulator.
Wettable powders (WP) may be prepared by mixing a composition of the disclosure with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine . Similar compositions may also be granulated to form water dispersible es (WG).
Granules (GR) may be formed either by granulating a mixture of a composition of the disclosure and one or more powdered solid diluents or carriers, or from preformed blank granules by absorbing a composition of the sure in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a composition of the disclosure (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, g agent or dispersing agent).
Dispersible trates (DC) may be prepared by dissolving a composition of the sure in water or an organic t, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallization in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a ition of the disclosure in an organic solvent. Suitable organic solvents for use in ECs include aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, ketones such as cyclohexanone or methylcyclohexanone, dimethyl amides of fatty acids such as C8-C10 fatty acid dimethylamide, N-alkylpyrrolidones such as N-methylpyrrolidone or N-octylpyrrolidone, chlorinated hydrocarbons, and alcohols such as ethanol, propanol, isopropanol, isopentane, ane, n-hexane, dimethoxymethane, benzyl l, benzyloxyethanol, alkylene ates such as ethylene carbonate and propylene carbonate, yethanol, butanol, isobutanol, cyclohexane, cyclohexanol, ethylenecarbonate, 1-phenylethylalcohol, 2-phenylethylalcohol, o-methoxyphenol and glycol ethers. Preferred c ts are glycol ethers. miting examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol nzyl ether, diethylene glycol monomethyl ether, lene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, and dipropylene glycol methyl ether. A preferred glycol ether solvent is dipropylene glycol methyl ether. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more surfactants, to spontaneously e a thermodynamically stable isotropic liquid formulation. A composition of the disclosure is present initially in either the water or the solvent/surfactant blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water (EW) or a water-in-oil (EO) system and may be suitable for mixing water-soluble and oil-soluble ides in the same formulation. An ME is suitable for on into water, either remaining as a microemulsion or forming an oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or ueous suspensions of finely divided ble solid particles of a composition of the disclosure. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the les settle.
Formulations may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing oams such as polyorganosiloxanes), sedimentation of active ingredients nding agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product ng (antifreezes), color (dyes/pigment sions), evaporation (evaporation retardants), and other formulation attributes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's on, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222. itions may be supplied in the form of a concentrate containing a high proportion of surfactants and matrix-forming agents, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs such as EWs and EOs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form s preparations which remain neous for a sufficient time to enable them to be applied by conventional spray equipment. c. Application A composition of the disclosure may be applied by any of the known methods of applying pesticidal compounds. For example, when applied to an animal, a composition may be applied to pests on an animal or to a locus of the pests on an animal or to any part of an animal. When applied to a plant, a composition may be applied to pests on a plant or to a locus of the pests or to any part of a plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems).
Compositions according to the disclosure are suitable for spot-on, shampoo formulations, or applied as a cream or paste formulations for use on animals, or dipping, pour-on or spray application on animals or plants where the spray application may be carried out, for example, using a pump spray or an aerosol spray (pressurized spray).
Compositions of the disclosure may also be applied with other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity. Other compounds having biological activity may provide a composition having a broader spectrum of activity or increased persistence at a locus; ize the activity or complement the activity (for example by increasing the speed of effect or ming repellency) of presently described compositions; or help to overcome or t the development of resistance to individual components.
The particular additional active ingredient will depend upon the intended y of the composition.
When used on plants, preferred other compounds having biological activity include pesticides. Examples of le pesticides e the following: a) Pyrethroids, such as hrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, pathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin or 5-benzylfurylmethyl-(E)- (1R,3S)-2,2-dimethyl(2-oxothiolanylidenemethyl)cyclopropane carboxylate; b) phosphates, such as profenofos, sulprofos, acephate, methyl parathion, os-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, , pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, uran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as enzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or lotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ctin, milbemycin, spinosad, azadirachtin or oram; h) Hormones or pheromones; i) Organochlorine compounds, such as lfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) nt agents, such as chloropicrin, dichloropropane, methyl bromide or metam; l) Neonicotinoid compounds, such as imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, nithiazine or flonicamid; m) Diacylhydrazines, such as tebufenozide, fenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; q) Pymetrozine; r) Spirotetramat, spirodiclofen or spiromesifen; s) Diamides, such as flubendiamide, chlorantraniliprole or aniliprole; t) Sulfoxaflor; u) Metaflumizone; v) Fipronil and Ethiprole; w) Pyrifluqinazon x) buprofezin; or y) 4-[(6-Chloro-pyridinylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furanone (DE 102006015467).
In addition to the major chemical s of pesticide listed above, other pesticides having ular targets may be ed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example, stemborer ic insecticides such as cartap, or hopper specific insecticides such as buprofezin for use in rice, may be employed. Alternatively insecticides or ides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovolarvicides , such as clofentezine, flubenzimine, iazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
Other preferred compounds having biological ty include fungicides. es of idal compounds which may be included in the composition of the invention are (E)-N-methyl[2-(2,5-dimethylphenoxymethyl)phenyl]methoxyiminoacetamide (SSF-129), 4-bromocyano-N,N-dimethyltrifluoromethylbenzimidazolesulfonamide , ?-[N-(3-chloro-2,6-xylyl)methoxyacetamido]-?-butyro lactone, 4-chlorocyano-N,N-dimethylp-tolylimidazolesulfonamide (IKF-916, cyamidazosulfamid), 3dichloro-N-(3-chloroethylmethyloxopropyl) benzamide (RH-7281, de), N-allyl-4,5,-dimethyl trimethylsilylthiophenecarboxamide (MON65500), N-(1-cyano-1,2-dimethylpropyl)- 2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxypyridyl)- ropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oride, copper oxyquinolate, copper sulfate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di pyridyl disulfide ioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propylbenzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, irimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl-(Z)—N-benzyl-N-([methyl(methylthioethylideneamino-oxycarbonyl )amino]thio)-ß-alaninate, azole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, amid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin e, fentin hydroxide, ferbam, ferimzone, fhiazinam, fludioxonil, f umetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, tpyr, guazatine, nazole, yisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine tate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoximmethyl , 54, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-iso-propyl, nuarimol, ofurace, organomercury nds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-A1, orus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, thanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, ethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, ndazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, anate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb, ziram; 1,3-Dimethyl-1H- pyrazolecarboxylic acid (4'-methylsulfanyl-biphenylyl)-amide, 1,3-Dimethyl-1H- pyrazolecarboxylic acid (2-dichloromethyleneethylmethyl-indanyl)-amide, and 1,3-Dimethyl-4H-pyrazolecarboxylic acid [2-(2,4-dichloro-phenyl)methoxy- 1-methyl-ethyl]-amide. The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against orne, soil-borne or foliar fungal pathogens.
When used in combination with other a ctive ingredients on plants, compositions of the invention are preferably used in combination with a pyrethroid such as lambda-cyhalothrin. Compositions of the invention are preferably used in combination with an insecticide ist. Insecticide synergists generally block the lic systems that would otherwise break down insecticide molecules, thereby increasing the efficiency of a ide in a formulation. Non-limiting examples of synergists include piperonyl de, N-octyl bicycloheptene dicarboximide (MGK-264), S-421, sesamex, safroxan and dodecyl imidazole. More preferably, itions of the invention may be used in ation with lambda-cyhalothrin and a synergist. More preferably, when used in combination with other active ingredients on plants, compositions of the invention are ECs comprising trisiloxane surfactants and sol-gel precursors as described in Section IbA, and further comprise lambda-cyhalothrin and nyl butoxide.
Still other preferred compounds having biological activity include herbicides.
Suitable herbicides and growth regulators for inclusion in the compositions will depend upon the intended target and the effect ed.
When used on animals, preferred other compounds having biological activity may include anthelmintic agents. Such anthelmintic agents include, compounds selected from the macrocyclic lactone class of nds such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives as described in EP-357460, EP-444964 and EP-594291. Additional anthelmintic agents e semisynthetic and biosynthetic avermectin/milbemycin derivatives such as those described in U.S. Pat. No. 5,015,630, 5944 and WO-9522552. Additional anthelmintic agents include the benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, dazole, and other members of the class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, el pamoate, oxantel or morantel. Additional anthelmintic agents include flukicides, such as triclabendazole and clorsulon and the cestocides, such as praziquantel and epsiprantel.
Other red compounds having biological activity on an animal may include other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide and the like; neonicotinoids such as imidacloprid and the like. Other examples of such biologically active compounds include but are not restricted to the following: Organophosphates: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, fos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimfos, famphur, phos, fenitrothion, fensulfothion, on, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacriphos, methamidophos, methidathion, methyl-parathion, hos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, hos, proetamphos, prothiofos, pyraclofos, penthion, quinalphos, sulprophos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion. ates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, yl, 5-methyl-m-cumenylbutyryl(methyl)carbamate, , pirimicarb, propoxur, thiodicarb, thiofanox, mate, UC-51717.
Pyrethroids: acrinathin, rin, alphametrin, 5-benzylfurylmethyl(E)-(1R)- cis-2,2-dimethyl(2-oxothiolanylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, a-cypermethrin, ypermethrin, bioallethrin, bioallethrin((S)-cyclopentylisomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, thrin, cythithrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, ethofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, luthrin, cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, Zeta-cypermethrin.
Arthropod growth regulators: a) chitin synthesis inhibitors: lureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, oxuron, umuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, ole, chlorfentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenoids: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis tors: spirodiclofen.
Other rasitics: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, den, diafenthiuron, DBI-3204, in, oxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, ethofenprox, quin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, f ufenzine, flufenprox, fluproxyfen, halofenprox, hydramethylnon, IKI-220, kanemite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pirydaryl, propargite, protrifenbute, pymethrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, dine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, verbutin, vertalec, yl-5301.
Fungicides: acibenzolar, aldimorph, ampropylfos, andoprim, azole, azoxystrobin, benalaxyl, benomyl, hos, blasticidin-S, ux mixture, bromuconazole, bupirimate, carpropamid, captafol, captan, carbendazim, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, copper oxychloride, copper salts, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, cyprofuram, RH-7281, diclocymet, diclobutrazole, diclomezine, dicloran, difenoconazole, RP-407213, dimethomorph, domoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, nam, fludioxonil, over, flumorf/flumorlin, fentin ide, fluoxastrobin, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetylaluminium , furalaxyl, tapyr, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, krsoxim-methyl, eb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin/fenominostrobin, metrafenone, myclobutanil, neo-asozin, nicobifen, orysastrobin, oxadixyl, penconazole, pencycuron, probenazole, prochloraz, ocarb, propioconazole, proquinazid, prothioconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, , tebuconazole, tetrconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, il, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin, vinclozin.
Biological agents: Bacillus thuringiensis ssp i, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, virus and fungi.
Bactericides: chlortetracycline, oxytetracycline, streptomycin.
Other biological agents: enrofloxacin, febantel, penethamate, moloxicam, cefalexin, kanamycin, pimobendan, terol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.
The following examples are ed to trate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the ques disclosed in the examples that follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.
Example 1. Preparation and Efficacy of Pesticidal Composition Comprising Trisiloxane and Tetraethyl Orthosilicate A pesticidal composition was prepared by mixing the Silibase 2848 trisiloxane silicon surfactant with the gel-forming sor thyl orthosilicate (TEOS) to form an emulsifiable liquid concentrate (EC) composition comprising 99% Silibase 2848 and 1% TEOS. The EC composition was then diluted in water to generate a composition for spraying on plants or s.
The efficacy of the prepared composition was evaluated against various plant pests (Tables 1-7). In short, plants infested with various pests were sprayed with the prepared diluted formulation, and % mortality of the pests was recorded.
Table 1. Efficacy against bird cherry oat aphid (Rhopalosiphum padi) on barley in the indoor pot test.
MORTALITY [%] Percentage by 1 hour after 2 days after weight treatment treatment Control: Silibase 2848 0.15% 80.2 92.4 ition according to the 0.15% 100 100 present Example 1 The results in Table 1 demonstrate that a composition comprising a trisiloxane surfactant with TEOS is more efficient at controlling pests when compared to a formulation comprising a similar amount of trisiloxane alone.
Table 2. Efficacy against red spider mite (Tetranychus urticae) on strawberry in field trials.
Control of larvae, nymphs and adults 2 weeks after treatment 4 weeks after treatment Composition according to 96.3 81.0 Example 1 (0.2%) Positive control: 95.4 87.2 oximate SC (1.25 l/ha) Application rate: 500 L/ha Table 3. Efficacy against Black bean aphid (Aphis fabae) on beetroot in field trials. 3 days after 7 days after 14 days after treatment treatment treatment Composition ing to 93.4 100 100 Example 1 (0.1%) Positive control: 98.7 100 100 pirimicarb WG (0.35 kg/ha) Application rate: 500 L/ha Table 4. Efficacy against cabbage aphid (Brevicoryne brassicae) on cabbage in field trials 3 days after 7 days after 14 days after ent treatment treatment Composition ing to 92.6 100 100 Example 1 (0.1%) Positive control: 87.0 99.3 98.7 pirimicarb WG (0.35 kg/ha) Application rate: 500 L/ha Table 5. Efficacy against red spider mite (Tetranychus e) on chrysanthemum in greenhouse trials. 3 days after treatment 7 days after treatment Composition according to 98.6 97.0 Example 1 (0.2%) Positive control: 0.0 93.6 Abamectin 018EC (0.05%) Application rate: 500 L/ha Table 6. Efficacy against common scale larvae (Parthenolecanium pomeranicum) on yew ) in field trial. 3 days after 7 days after 14 days after treatment treatment treatment Composition according to 92.3 98.7 92.2 Example 1 (0.2%) ve control: 0.0 71.8 22.6 Spirotetramat 100SC (0.075%) Application rate: 500 L/ha Table 7. Efficacy against greenhouse whitefly (Trialeurodes vaporariorum) on gerbera in field trial.
Composition according to 1 day after 3 days after 7 days after Example 1 (0.2%) treatment ent treatment 91.3% 90.8% 92.6% Positive control: 94.9% 93.6% 93.8% Imidacloprid 200 SL 0.08% The results in Tables 2-7 demonstrate that a composition as prepared in this e is more efficient or at least as efficient at controlling various pests when compared to formulations comprising pesticides with mode of action other than a physical mode of action. In the case of red spider mites on chrysanthemum and common scale larvae on yew, the composition bed herein was almost completely effective at killing the pests 3 days after treatment, whereas positive control formulations comprising conventional active agents such as Abamectin and Spirotetramat were not effective at all.
Tables 8-9 illustrate the efficacy of the prepared composition t various pests on s. The composition according to Example 1 was sprayed as a prepared diluted formulation directly to the vent of infested birds. Each bird was scored for mites using visual and photographic methods, both pre- and posttreatment.
Scoring was conducted on the following scale: 0: 0 mites 1: 1-10 mites 2: 11-100 mites 3: >100 mites Table 8. Efficacy against northern fowl mite (Ornithonyssus sylviarum) in deep litter housing system.
Treatment Percentage by weight Day 0 (treatment) 7 DAT Composition according to 0.3% 3 0 Example 1 - BIRD 1 Composition according to 0.3% 2 0 Example 1 - BIRD 2 Composition according to 0.3% 2 0 Example 1 - BIRD 3 Composition according to 0.3% 3 0 e 1 - BIRD 4 Control - BIRD 1 --- 2 1 Control - BIRD 2 --- 2 2 Control - BIRD 3 --- 1 2 Control - BIRD 4 --- 3 2 DAT: days after treatment The results in Table 8 rate that a composition ing to Example 1 was more effective or at least as effective at controlling various pests when compared to ations comprising pesticides with mode of action other than a physical mode of action.
Table 9. Efficacy against red poultry mite (Dermanyssus gallinae) in battery cage housing system.
Treatment Percentage 5 DAT 10 DAT eated by weight ment) after 5 days) Composition according to 0.6% 70% 85% Example 1 Control untreated --- 0% 0% DAT: days after ent The results in Table 9 trate that a composition according to Example 1 is very effective in controlling red poultry mites when applied to typical hiding places, where mites aggregate (cracks, crevices and hollow places (e.g. in troughs and feeders, walls, floors, etc.).
Example 2. Preparation and Determination of Efficacy of Pesticidal Composition Comprising a Synergist in Addition to Trisiloxane and TEOS A pesticidal ition was prepared by mixing the composition described in Example 1 with the synergist piperonyl butoxide (PBO) to form a composition sing 90% of the composition of Example 1, and 10% PBO.
The resulting composition was prepared for administration onto plants by mixing 0.4 liters of the composition and 0.12 liters of the pyrethroid pesticide Karate Zeon 050CS in 200 liters of water. A control formulation comprising only 0.12 liters of the pyrethroid pesticide Karate Zeon 050CS in 200 liters of water was also prepared for comparison. The efficacy of the resulting spray formulations was evaluated against pollen beetle ethes aeneus) on spring oilseed rape (Table 10). In short, plants ed with pollen beetle were sprayed with the prepared formulations, and % mortality of the pests was recorded.
Table 10. Efficacy against pollen beetle (Meligethes aeneus) on Spring oilseed rape Formulation Mortality [%] 2 days after 4 days after 6 days after treatment ent treatment Control: Karate 69.31 68.57 53.65 Zeon 050CS Karate Zeon 87.15 83.26 69.18 050CS + Composition according to Example 2 The results in Table 10 demonstrate that a composition as prepared in this Example is more efficient at controlling pests when compared to ations comprising the pesticide alone.
Example 3. Preparation and Determination of Efficacy of Pesticidal Composition Comprising insecticides in addition to Trisiloxane and TEOS.
A pesticidal composition was prepared by mixing the composition bed in Example 1 with a ready-to-use solution of microcapsulated lambda-cyhalothrin and fipronil. The resulting composition was prepared for administration onto a bed frame by mixing 2 ml of the composition described in Example 1 and 1.0 liter microcapsulated lambda-cyhalothrin and fipronil spray solution (0.1%).
A control formulation comprising 1.0 liter microcapsulated lambda-cyhalothrin and fipronil spray solution (0.1%) was also prepared for ison as the control.
The efficacy of the resulting spray formulations was evaluated on bed bugs (Cimex lectularius) -males, females, strain resistant to pyrethroids (Table 11). In short, bed frames of infested beds were sprayed with the prepared formulations and % of ity of the pests was recorded.
Table 11. Efficacy against bed bugs (Cimex lectularius) when applied to bed frame.
Formulation Mortality [%] Immediately after 24 hours after 48 hours after treatment treatment treatment l: 0.1% spray 0% 15% 55% solution of capsulated -cyhalothrin and fipronil 0.1% spray solution of 100% 100% 99% capsulated lambdacyhalothrin and fipronil + 0.2% Composition ing to Example 1 The results in Table 11 demonstrate that a composition as prepared in this Example is more efficient at lling pest populations harboring in inaccessible locations, when compared to formulations comprising the pesticide alone.
Example 5. Preparation and Determination of Efficacy of Pesticidal Emulsion Concentrate Comprising Trisiloxane and Tetraethyl Orthosilicate with Pyriproxyfen.
A pesticidal composition can be prepared by mixing a trisiloxane silicone surfactant with TEOS and pyriproxyfen to form an emulsifiable liquid concentrate (EC) as set forth in Table 14. The EC composition can then be diluted in water to generate a composition comprising about 2% oxane ne surfactant for spraying on .
Table 14. Pesticidal composition Ingredient Concentration (%) Pyriproxyfen 98% 2.5% w/w C12-15 Alkyl Benzoate 6.0% w/w TEOS 0.1% w/w Silwet 408 91.4% w/w The foregoing merely illustrates the principles of the disclosure. Various modifications and alterations to the described embodiments will be apparent to those skilled in the art in view of the teachings . It will thus be appreciated that those skilled in the art will be able to devise us compositions and methods which, although not explicitly shown or described herein, embody the principles of the disclosure and are thus within the spirit and scope of the present disclosure. From the above description and gs, it will be understood by those of ordinary skill in the art that the particular ments shown and described are for purposes of illustrations only and are not intended to limit the scope of the present disclosure.
References to details of particular embodiments are not intended to limit the scope of the disclosure.
Claims (12)
1. A non-therapeutic use of a composition comprising: a. at least one oxane surfactant having Formula (I): wherein R is -(CH2)3-(OCH2CH2)nOR1; R1 is -H, -CH3, or -O(O)CCH3; and n is 2 to 20; and b. a matrix-forming agent in a form of at least one metal or metalloid de sol-gel precursor, preferably silicon or titanium alkoxide sol-gel precursor, wherein the combination of the constituents a. and b. has pesticidal properties, for controlling and/or killing a pest or a pathogen by ng the composition to a pest, a pathogen or a locus.
2. The use according to claim 1, wherein the at least one trisiloxane surfactant is present in the composition in an amount of 0.1% to 99.9% (wt/wt).
3. The use according to claim 1, wherein the at least one sol-gel sor is present in the composition in an amount of 0.1% to 5% (wt/wt).
4. The use according to claim 1, wherein the at least one sol-gel sor is selected from the group consisting of tetraethyl orthosilicate, tramethyl ilicate, and combinations thereof.
5. The use according to claim 4, wherein the sol-gel precursor is tetraethyl orthosilicate.
6. The use according to claim 5, n the at least one trisiloxane surfactant is present in the composition in an amount of about 99% (wt/wt), and tetraethyl orthosilicate is present in an amount of about 1% (wt/wt).
7. The use according to claim 1, n the composition further comprises a pesticide.
8. The use accord ing to claim 1, n the composition further comprises an insecticide synergist selected from the group consisting of piperonyl butoxide N- octyl oheptene dicarboximide (MGK-264), S-421, sesamex, safroxan . dodecyl imidazole, and combinations thereof.
9. The use according to claim 8, wherein the insecticide synergist is piperonyl butoxide.
10. The use according to any one of the preceding claims 1 to 9, wherein the composition is applied to a pest, a pathogen, or a locus in a form d in water as a diluted pesticidal composition comprising trisiloxane surfactant in an amount of 0.01 % to 4% (wt/wt).
11. A non-therapeutic method of controlling a pest or a pathogen, the method comprising applying a composition de fined in any one of claims 1 to 10 to a pest, a pathogen, or a locus, wherein the method is not carried out on the human or animal body.
12. A erapeutic method of killing a pest, the method comprising applying a composition defined in any one of claims 1 to 10 to a pest, wherein the method is not carried out on the human or animal body.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462063504P | 2014-10-14 | 2014-10-14 | |
| PCT/US2015/055578 WO2016061259A1 (en) | 2014-10-14 | 2015-10-14 | Pesticide formulations having physical mode of action |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NZ730867A NZ730867A (en) | 2023-09-29 |
| NZ730867B2 true NZ730867B2 (en) | 2024-01-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12568966B1 (en) | 2025-04-30 | 2026-03-10 | Sanjay Venkatesh Modgi | Aqueous biocidal composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12568966B1 (en) | 2025-04-30 | 2026-03-10 | Sanjay Venkatesh Modgi | Aqueous biocidal composition |
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