WO2007034275A2 - Formulations for improved stability of pest control agents - Google Patents
Formulations for improved stability of pest control agents Download PDFInfo
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- WO2007034275A2 WO2007034275A2 PCT/IB2006/002541 IB2006002541W WO2007034275A2 WO 2007034275 A2 WO2007034275 A2 WO 2007034275A2 IB 2006002541 W IB2006002541 W IB 2006002541W WO 2007034275 A2 WO2007034275 A2 WO 2007034275A2
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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
- A01N25/02—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
Definitions
- the present invention is directed to increasing the stability of pest control agents that degrade after application as a result of exposure to environmental factors, and more particularly, to the use of vegetable oils, modified vegetable oils, or vegetable oil derivatives in formulations to protect the agents from the damaging environmental factors.
- pest control compositions are often made less effective or ineffective after application due to environmental factors. These environmental factors, including sunlight, oxidation, and rain, greatly increase cost to users because they require the user to make-up for the ever decreasing effectiveness of the pest control composition. Some users try to abate the damaging effects of the environmental factors by applying the product more frequently or by using a more concentrated dosage of the pest control agent. However, users could better control their costs due to environmental factors by using a pest control composition with better efficacy in the face of the environmental factors. As such, improved pest control compositions and methods of making such compositions are needed.
- the present invention comprises a pest control composition, comprising: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent.
- the present invention comprises a pest control composition, comprising: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; c) a pest control agent; and d) an emulsifier.
- the present invention comprises a pest control composition comprising a vegetable oil and a pest control agent.
- the present invention comprises a pest control composition
- a pest control composition comprising: a) sunflower oil; b) water; and c) codling moth granulovirus.
- the present invention comprises a method of making a pest control composition
- a method of making a pest control composition comprising: a) adding a pest control agent to a first oil phase, wherein the first oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; and b) adding the combination of (a) to a second phase.
- the present invention comprises a) adding an emulsifier to an oil phase, wherein the oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; b) adding a pest control agent with water; and c) adding the combination of (a) and (b) to water.
- the present invention comprises a method for applying a pest control composition, comprising spraying a pest control composition onto an article, wherein the composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent.
- Fig. 1 depicts the influence of UV-B radiation on pyrethrin degradation
- Fig. 2 depicts the effect of sunflower oil on pyrethrin degradation by UV-B after a 2 hour exposure.
- the present invention is directed to increasing the stability of pest control agents that degrade after application as a result of exposure to environmental factors, and more particularly, to the use of vegetable oils, modified vegetable oils, or vegetable oil derivatives in formulations to protect the agents from damaging environmental factors.
- the pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent.
- the second phase comprises water.
- the composition is an emulsion in which the first oil phase is the discontinuous phase.
- the pest control agent or agents for example, insecticides
- the pest control agents are made more effective.
- the improved persistence of the emulsion applied to vegetation, due to the hydrophobic oil droplets inhibits wash-off due to rain.
- the oil provides a level of protection from ultraviolet light (UV).
- UV ultraviolet light
- the present pest control composition provides at least an equivalent level of protection to conventional formulations but at a reduced concentration.
- a user decides to use the current pest control composition at conventional concentrations, then he will benefit from the current invention because he will be required to apply the current pest control composition less often. For example, if a user with a conventional formulation and concentration needs to apply the pesticide three times a month to achieve the desired results, then that same user would be only be required to reapply the current pest control composition two or less times in that same time period and would achieve at least the same results.
- the pest control composition further comprises a third phase, wherein the third phase comprises water.
- the third phase (water) is the continuous phase.
- the first oil phase comprises sorbitan trioleate.
- the composition comprises a water-in- oil-in-water emulsion. Not to be limited by theory, even though the third phase of water is present it is believed that the pest control agent remains in the oil phase. Advantages of this embodiment include the ability to protect hydrophilic pest control agents which would normally not remain associated with the hydrophobic oil phase and thus would not have the advantages of its protection from environmental factors.
- the composition is a dispersion.
- solutions of pest control agents in vegetable oils and their derivatives are useful if the solutions are emulsifiable and give emulsions on dilution into water (aka: emulsifiable concentrate "EC") or the solutions are sprayed undiluted, giving oil droplets on the target without water being used at all.
- EC emulsifiable concentrate
- the second phase comprises a second oil phase and in a further embodiment, the second oil phase is selected from the group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; and the oil of the second oil phase is different from the oil in the first oil phase.
- Modified vegetable oil can include, for example, methylated, ethylated, and butylated seed oils.
- Derivatives of vegetable oils can include, for example, sorbitan, alkyl esters, and others. These are generally formed by chemical modification, for example, esterif ⁇ cation.
- the addition of the functional groups to both modified vegetable oils and derivatives of vegetable oils can aid in the emulsif ⁇ cation of the pest control agent.
- the first and second oil phases form a dispersion of oil within oil.
- the oil in the first oil phase comprises sunflower oil.
- the vegetable oil is preferably non-repellent/non-anti-feedant to the pest.
- the vegetable oil would stimulate feeding and be palatable so as to increase uptake by feeding.
- the oil is chosen to be compatible with the pesticide so as not to cause decomposition of a chemical agent or make biological agents non-viable.
- Suitable oils include natural oils, natural oil derivatives and other like materials used in food processing, cosmetics, de ⁇ natological products or pharmaceutical preparations.
- the pest control agent could be a synthetic chemical, a biopesticide such as an extract from a natural source or a chemically modified natural product, or a biological agent such as a virus particle.
- the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, and synthetic chemicals.
- the pest control agent is selected from the group consisting of: virus, fungus, bacteria, pyrethrin, and codling moth granulovirus.
- the pest control agent could also include products or sub-products obtained by bio-fermentation or genetics, for instance, protein toxins, mycotoxins, metabolites, vitamins, amino-acids, sexual or aggregation hormones, elicitors, extracts, phenols, etc.
- Some of the embodiments of the invention are useful for pest control agents that include but are not limited to, those: a) soluble in the vegetable oil system (by way of example and not limitation, natural pyrethrins), b) used as a concentrated wet-cake of insoluble particles in water, which may be further diluted with water before formulating this way if desired (by way of example and not limitation, codling moth granulovirus), c) used as a dry powder to be dispersed into the vegetable oil system, and d) aqueous solutions, that are first emulsified into the vegetable oil then further dispersed to give a multiple emulsion.
- a) soluble in the vegetable oil system by way of example and not limitation, natural pyrethrins
- b) used as a concentrated wet-cake of insoluble particles in water which may be further diluted with water before formulating this way if desired (by way of example and not limitation, codling moth granulovirus)
- the first oil phase comprises a vegetable oil selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safflower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives.
- the vegetable oil comprises sunflower oil and the pest control agent comprises codling moth granulovirus.
- the composition is applied to a substrate by spraying.
- the substrate can comprise any surface where there would be a need for pest removal.
- the substrate could be vegetation, foliage, crops, wood, cement, etc.
- the specific spraying method comprises electric field effect technology (EFET) or ultra-low volume application (ULV). Additional methods of applying the composition to the substrate are known to those skilled in the art and are within the purview of this invention.
- composition further comprises a further UV blocking agent known to those skilled in the art, such as sunscreen and combinations of anti-oxidants and sunscreen.
- a pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; c) a pest control agent; and d) an emulsifier.
- the first oil phase comprises vegetable oil and the emulsifier comprises a derivative of vegetable oil.
- the first oil phase comprises sunflower oil and the emulsifier comprises sorbitan trioleate.
- the composition further comprises an additional UV blocking agent.
- the pest control agent comprises a virus.
- the pest control composition could contain water and/or residual water or water could be added to the pest control agent resulting in a water-in-oil-in-water emulsion.
- a pest control composition comprises a vegetable oil and a pest control agent.
- the vegetable oil is selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, saf ⁇ lower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives.
- the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, synthetic chemicals, and derivatives.
- the vegetable oil comprises sunflower oil and the pest control agent comprises codling moth granulovirus.
- the pest control composition further comprises a diluent.
- the diluent comprises water.
- the composition comprises an emulsion.
- the composition further comprises an additional UV blocking agent.
- a pest control composition comprises: a) sunflower oil; b) water; and c) codling moth granulovirus.
- the composition further comprises an additional UV blocking agent.
- the invention comprises a method of making a pest control composition
- a method of making a pest control composition comprising: a) adding a pest control agent to a first oil phase, wherein the first oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives, with a pest control agent; and b) adding the combination of (a) to a second phase.
- the second phase comprises water.
- the second phase comprises a second oil phase, wherein the second oil phase is selected from the group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; and the oil of the second oil phase is different from the oil in the first oil phase.
- the first oil phase comprises a vegetable oil selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, saf ⁇ lower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives.
- the method of making the pest control composition further comprises adding a third phase.
- the third phase comprises water.
- the composition comprises a water-in-oil-in- water emulsion.
- the pest control agent contains residual water.
- the pest control agent comprises a virus.
- the pest control composition further comprises an additional UV blocking agent.
- a method of making a pest control composition comprises: a) adding an emulsifier to an oil phase, wherein the oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; b) adding a pest control agent with water; and c) adding the combination of (a) and (b) to water.
- the oil phase comprises sunflower oil and the emulsifier comprises a vegetable oil derivative.
- the emulsifier comprises sorbitan trioleate.
- a method of applying a pest control composition comprises spraying a pest control composition onto a substrate wherein the pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent.
- the second phase of the composition comprises water.
- the step of spraying comprises electric field effect technology.
- the step of spraying comprises ultra-low volume application.
- the composition is at a lower concentration than conventional formulations. In an additional embodiment, the composition requires a lower number of applications than conventional formulations. In another embodiment, the composition further comprises an additional UV blocking agent.
- the composition further comprises a third phase.
- the third phase comprises water.
- the second phase comprises water and the water comes from the pest control agent.
- the composition further comprises an emulsifier.
- Example 1 Oil emulsion carrier base for virus particles
- Soprophor FLK (dispersing agent commercially available from Rhodia Novecare) into the water. Then, add the sunflower oil into the Soprophor/water mixture with high shear mixing. Measure the particle size after 30 seconds (it will approximately be 15-20 ⁇ ). Measure again at 1 minute (the particle size will be approximately 8-12 ⁇ ). Measure again after approximately 90 seconds (the particle size will be approximately 5-8 ⁇ with no flocculation). Laser-particle size analysis will show a measurement of D10-2.371 ⁇ , D50-4.324 ⁇ , D90-7.715 ⁇ . Add a drop of anti-foam.
- Rhodopol G xanthan gum commercially available from Rhodia Novecare
- Example 2 (Pest control formulation with codling moth granulovirus)
- the Malvern laser particle size analysis result is:
- a fluorescent tube (Philips Ultraviolet-B, TL40W/12RS) having an emission spectrum of 280-320 nm is used to provide UV-B light.
- the tube is placed in a dark room with a stable temperature of 22-24 °C. Open borosilicate 6 cm-diam.
- Petri dishes are placed on pre-indicated places under the UV-tube. The distance between the Petri dish and the underside of the UV-B tube is 14.5 cm.
- the level of irradiance is measured by a precalibrated spectroradiometer (Gr ⁇ bel, Düsseldorf, Germany). The level is
- the pyrethrin sample used in this test is Pyrethrum Extract Pale, which is a highly refined extract with 50% w/w total pyrethrins.
- the other 50% of the composition is described as "vegetable materials plus isoparaffm solvent.”
- maximal absorbance of UV radiation may be in the 225 nm range which is not covered by the UV-B fluorescent tube.
- the 225 nm range may be present in natural sunlight.
- the reproducibility of the data is good: duplicate injections of the same samples give insignificant differences.
- Sunflower oil retards pyrethrin degradation (Fig. 2).
- a pest control composition for application to a substrate comprises a pest control agent and a protective agent selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil, wherein, in use, the pest control composition forms upon the substrate droplets or globules of the protective agent and the pest control agent is housed within or covered by the protective agent droplets or globules (or "igloos") to protect the pest control agent from environmental effects such as sunlight, oxidation and rain.
- a protective agent selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil
- the composition may comprise an emulsion of the protective agent as a first phase within a second phase with the pest control agent being contained within the protective agent.
- a pest control agent such as codling moth granulovirus that is insoluble in the first phase may be dispersed as particulate matter within the first phase:
- a pest control agent such as codling moth granulovirus may be associated with a further agent such as sorbitan trioleate and then dispersed within the first phase so that the composition comprises droplets of the further agent containing the pest control agent and those droplets are dispersed within the first phase.
- the pest control agent is provided within the droplets or globules of the first phase so that the first phase directly encapsulates or houses the pest control agent and protects it from environmental effects such as sunlight, oxidation and rain
- the composition may comprise a liquid carrier carrying the pest control agent and the liquid carrier may be combined or mixed with protective agent to form an emulsion of protective agent within the liquid carrier such that, in use when applied to the substrate droplets or globules of protective agent coat or otherwise protect the pest control agent.
- a water-insoluble pest control agent such as pyrethrin plus synergist may be dissolved in a solvent (or a pest control agent such as carpovirusine may be dispersed in a liquid) and then combined or mixed with the protective agent and an emulsifier to form an emulsion of protective agent in water such that, in use, when the composition is applied to the substrate and dries as the solvent evaporates, droplets or globules of protective agent are left coating or otherwise protecting the pest control agent from environmental effects such as sunlight, oxidation and rain.
- Any suitable form of vegetable oil or derivative may be used and the examples give herein should not be considered to represent an exhaustive list. Unsaturated, saturated and polyunsaturated vegetable oils may be used.
- Polyunsaturated vegetable oils have better UV blocking characteristics than unsaturated vegetable oils.
- a vegetable oil modified vegetable oil or vegetable oil derivative is used. It may, however, be possible to use any biological oil (“bio-oil”), modified biological oil or biological oil derivative which is environmentally friendly, which is not significantly detrimental to the substrate to which the spray is to be applied, and which is palatable to the target of the pesticide.
- a biological oil or “bio-oil” is an oil derived from or based on a biological source, such as a plant, vegetable, nut, seed, animal or fish. For example, it may be possible to use a fish oil, modified fish oil or fish oil derivative.”
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Abstract
Pest control compositions are provided having: a) a first oil phase, wherein the first oil phase is selected from a group; b) a second phase; and c) a pest control agent. Also provided are methods of making a pest control composition by: a) combining a first oil phase, wherein the first oil phase is selected from a group, with a pest control agent; and b) adding the combination to a second phase. Additionally provided are methods of applying a pest control composition, by spraying a pest control composition onto a substrate, wherein the composition comprises: a) a first oil phase; b) a second phase; and c) a pest control agent.
Description
Formulations for Improved Stability of Pest Control Agents
CROSS-REFERENCES TO RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Application 60/718,432 which was filed September 19, 2005 and U.S. Provisional Application
60/731,439 filed October 28, 2005 and U.S. Patent Application Serial No. 11/508,546 filed August 23, 2006. The entire contents of those applications are incorporated by reference.
FIELD OF THE INVENTION
The present invention is directed to increasing the stability of pest control agents that degrade after application as a result of exposure to environmental factors, and more particularly, to the use of vegetable oils, modified vegetable oils, or vegetable oil derivatives in formulations to protect the agents from the damaging environmental factors.
BACKGROUND OF THE INVENTION
In the pest control market, the efficacy of a pest control composition is highly valued. Unfortunately, pest control compositions are often made less effective or ineffective after application due to environmental factors. These environmental factors, including sunlight, oxidation, and rain, greatly increase cost to users because they require the user to make-up for the ever decreasing effectiveness of the pest control composition. Some users try to abate the damaging effects of the environmental factors by applying the product more frequently or by using a more concentrated dosage of the pest control agent. However, users could better control their costs due to environmental factors by using a pest control composition with better efficacy in the face of the environmental factors. As such, improved pest control compositions and methods of making such compositions are needed.
SUMMARY OF THE INVENTTON
In view of the need for improved pest control compositions and methods of making and using the comppsitions, the present invention therefore provides improvements over the currently available agents and methods.
In one embodiment, the present invention comprises a pest control composition, comprising: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent. In an additional embodiment, the present invention comprises a pest control composition, comprising: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; c) a pest control agent; and d) an emulsifier.
In another embodiment, the present invention comprises a pest control composition comprising a vegetable oil and a pest control agent.
In an additional embodiment, the present invention comprises a pest control composition comprising: a) sunflower oil; b) water; and c) codling moth granulovirus.
In another embodiment, the present invention comprises a method of making a pest control composition comprising: a) adding a pest control agent to a first oil phase, wherein the first oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; and b) adding the combination of (a) to a second phase.
In an additional embodiment, the present invention comprises a) adding an emulsifier to an oil phase, wherein the oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; b) adding a pest control agent with water; and c) adding the combination of (a) and (b) to water.
In one additional embodiment, the present invention comprises a method for applying a pest control composition, comprising spraying a pest control composition onto an article, wherein the composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent.
These and additional embodiments and advantages may be more fully apparent in view of the drawings and detailed description.
BRIEF DESCRIPTION OF THF, DRAWINGS
The following detailed description will be more fully understood in view of the drawings in which:
Fig. 1 depicts the influence of UV-B radiation on pyrethrin degradation; and
Fig. 2 depicts the effect of sunflower oil on pyrethrin degradation by UV-B after a 2 hour exposure.
The embodiments set forth in the drawings are illustrative in nature and are not intended to be limiting of the invention defined by the claims. Moreover, individual features of the drawing and the invention will be more fully apparent and understood in view of the detailed description.
DETAILED DESCRIPTION
The present invention is directed to increasing the stability of pest control agents that degrade after application as a result of exposure to environmental factors, and more particularly, to the use of vegetable oils, modified vegetable oils, or vegetable oil derivatives in formulations to protect the agents from damaging environmental factors.
In the agricultural pesticide market, users would greatly benefit from increased persistence of the pest control composition on the target area after spraying. As described herein, this can be accomplished by protecting the pest control agent within a pest control composition.
In one embodiment, the pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent. In another embodiment, the second phase comprises water. In a further embodiment, the composition is an emulsion in which the first oil phase is the discontinuous phase.
By incorporating the pest control agent or agents (for example, insecticides) into the oil phase of an emulsion based on a vegetable oil or mixture of vegetable oils, the pest control agents are made more effective. For example, the improved persistence of the emulsion applied to vegetation, due to the hydrophobic oil droplets, inhibits wash-off due to rain. Moreover, the oil provides a level of protection from ultraviolet light (UV). One experiment has even shown that about 130-140% more of a natural insecticide remained after brief UV-B exposure when mixed with a vegetable oil when compared with compositions without vegetable oil.
In addition, housing the pest control agent within the oil droplets impedes oxidation of the agents while still remaining palatable to pests. Due to the extra protection provided by the oil, the present pest control composition provides at least an equivalent
level of protection to conventional formulations but at a reduced concentration. In addition, if a user decides to use the current pest control composition at conventional concentrations, then he will benefit from the current invention because he will be required to apply the current pest control composition less often. For example, if a user with a conventional formulation and concentration needs to apply the pesticide three times a month to achieve the desired results, then that same user would be only be required to reapply the current pest control composition two or less times in that same time period and would achieve at least the same results.
This increased durability and stability of the agent after application translates into significant material and labor cost savings in the markets of use, and enhances the economics and attractiveness of "green," "natural" or "organic" pest control agents. The material savings are realized in that the pest control agents encapsulated in the oil droplets are dispersed in the emulsion so that resulting products require a reduced concentration to achieve an equivalent level of efficacy and/or remain efficacious for a longer period of time. In addition, while the pest control agent does last longer in the current pest control' composition, it still achieves complete environmental degradation and thus remains friendly to the environment.
In another embodiment, the pest control composition further comprises a third phase, wherein the third phase comprises water. In this embodiment, the third phase (water) is the continuous phase. In a further embodiment, the first oil phase comprises sorbitan trioleate. In another further embodiment, the composition comprises a water-in- oil-in-water emulsion. Not to be limited by theory, even though the third phase of water is present it is believed that the pest control agent remains in the oil phase. Advantages of this embodiment include the ability to protect hydrophilic pest control agents which would normally not remain associated with the hydrophobic oil phase and thus would not have the advantages of its protection from environmental factors.
In an additional embodiment, the composition is a dispersion. In addition, solutions of pest control agents in vegetable oils and their derivatives are useful if the solutions are emulsifiable and give emulsions on dilution into water (aka: emulsifiable concentrate "EC") or the solutions are sprayed undiluted, giving oil droplets on the target without water being used at all.
In another embodiment, the second phase comprises a second oil phase and in a further embodiment, the second oil phase is selected from the group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; and the oil of the
second oil phase is different from the oil in the first oil phase. Modified vegetable oil can include, for example, methylated, ethylated, and butylated seed oils. Derivatives of vegetable oils can include, for example, sorbitan, alkyl esters, and others. These are generally formed by chemical modification, for example, esterifϊcation. Also, the addition of the functional groups to both modified vegetable oils and derivatives of vegetable oils can aid in the emulsifϊcation of the pest control agent. In another embodiment, the first and second oil phases form a dispersion of oil within oil. In a further embodiment, the oil in the first oil phase comprises sunflower oil.
For pest control agents such as stomach-acting insecticides, the vegetable oil is preferably non-repellent/non-anti-feedant to the pest. Ideally, the vegetable oil would stimulate feeding and be palatable so as to increase uptake by feeding. The oil is chosen to be compatible with the pesticide so as not to cause decomposition of a chemical agent or make biological agents non-viable. Suitable oils include natural oils, natural oil derivatives and other like materials used in food processing, cosmetics, deπnatological products or pharmaceutical preparations.
Looking to the pest control agent, it could be a synthetic chemical, a biopesticide such as an extract from a natural source or a chemically modified natural product, or a biological agent such as a virus particle. In one embodiment, the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, and synthetic chemicals. In a further embodiment, the pest control agent is selected from the group consisting of: virus, fungus, bacteria, pyrethrin, and codling moth granulovirus. In another embodiment, the pest control agent could also include products or sub-products obtained by bio-fermentation or genetics, for instance, protein toxins, mycotoxins, metabolites, vitamins, amino-acids, sexual or aggregation hormones, elicitors, extracts, phenols, etc.
Some of the embodiments of the invention are useful for pest control agents that include but are not limited to, those: a) soluble in the vegetable oil system (by way of example and not limitation, natural pyrethrins), b) used as a concentrated wet-cake of insoluble particles in water, which may be further diluted with water before formulating this way if desired (by way of example and not limitation, codling moth granulovirus), c) used as a dry powder to be dispersed into the vegetable oil system, and d) aqueous solutions, that are first emulsified into the vegetable oil then further dispersed to give a multiple emulsion.
In another embodiment, the first oil phase comprises a vegetable oil selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safflower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives. In a further embodiment, the vegetable oil comprises sunflower oil and the pest control agent comprises codling moth granulovirus. In one embodiment, the composition is applied to a substrate by spraying. In additional embodiments, the substrate can comprise any surface where there would be a need for pest removal. For example, the substrate could be vegetation, foliage, crops, wood, cement, etc. In a further embodiment the specific spraying method comprises electric field effect technology (EFET) or ultra-low volume application (ULV). Additional methods of applying the composition to the substrate are known to those skilled in the art and are within the purview of this invention.
In another embodiment, the composition further comprises a further UV blocking agent known to those skilled in the art, such as sunscreen and combinations of anti-oxidants and sunscreen.
In one embodiment, a pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; c) a pest control agent; and d) an emulsifier. In another embodiment, the first oil phase comprises vegetable oil and the emulsifier comprises a derivative of vegetable oil. In a further embodiment, the first oil phase comprises sunflower oil and the emulsifier comprises sorbitan trioleate. In another embodiment, the composition further comprises an additional UV blocking agent. In another embodiment, the pest control agent comprises a virus. In one embodiment, the pest control composition could contain water and/or residual water or water could be added to the pest control agent resulting in a water-in-oil-in-water emulsion.
In one embodiment, a pest control composition comprises a vegetable oil and a pest control agent. In a further embodiment, the vegetable oil is selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safϊlower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives. In an additional embodiment, the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, synthetic chemicals, and derivatives. In one embodiment, the vegetable oil comprises sunflower oil and the pest control agent comprises codling moth granulovirus.
In another embodiment, the pest control composition further comprises a diluent. In a further embodiment, the diluent comprises water. In a further embodiment, the composition comprises an emulsion. In another embodiment, the composition further comprises an additional UV blocking agent. In one embodiment, a pest control composition comprises: a) sunflower oil; b) water; and c) codling moth granulovirus. In a further embodiment, the composition further comprises an additional UV blocking agent.
In another embodiment, the invention comprises a method of making a pest control composition comprising: a) adding a pest control agent to a first oil phase, wherein the first oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives, with a pest control agent; and b) adding the combination of (a) to a second phase. In one embodiment, the second phase comprises water.
In another embodiment, the second phase comprises a second oil phase, wherein the second oil phase is selected from the group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; and the oil of the second oil phase is different from the oil in the first oil phase. In a further embodiment, the first oil phase comprises a vegetable oil selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safϊlower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and derivatives. In another embodiment, the method of making the pest control composition further comprises adding a third phase. In a further embodiment, the third phase comprises water. In another embodiment, the composition comprises a water-in-oil-in- water emulsion. In one embodiment, the pest control agent contains residual water.
Where water is already present in the pest control agent (e.g. some viruses), additional water is not necessary to form a water-in-oil-in-water emulsion because the water within the pest control agent is enough to form a third phase. In this embodiment, vegetable oil derivatives that are useful as water-in-oil emulsifiers would be used to emulsify a water-based system into the vegetable oil system, which is then emulsified into water. Further, some vegetable oil derivatives are not fully miscible with vegetable oils and spontaneously self-emulsify in vegetable oils at higher concentrations (by way of example and not limitation, 10%), forming dispersions of oil within oil, such that droplets of vegetable oil derivative form within the vegetable oil emulsion droplet. This property can also be used to help prepare water-in-oil-in-water emulsions. In an additional
embodiment, the pest control agent comprises a virus. In a further embodiment, the pest control composition further comprises an additional UV blocking agent.
In one embodiment, a method of making a pest control composition comprises: a) adding an emulsifier to an oil phase, wherein the oil phase is selected from a group consisting of vegetable oil, modified vegetable oil, and vegetable oil derivatives; b) adding a pest control agent with water; and c) adding the combination of (a) and (b) to water. In another embodiment, the oil phase comprises sunflower oil and the emulsifier comprises a vegetable oil derivative. In a further embodiment, the emulsifier comprises sorbitan trioleate. In another embodiment, a method of applying a pest control composition, comprises spraying a pest control composition onto a substrate wherein the pest control composition comprises: a) a first oil phase, wherein the first oil phase is selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil; b) a second phase; and c) a pest control agent. In a further embodiment, the second phase of the composition comprises water. In another embodiment, the step of spraying comprises electric field effect technology. In an additional embodiment, the step of spraying comprises ultra-low volume application.
In another embodiment, the composition is at a lower concentration than conventional formulations. In an additional embodiment, the composition requires a lower number of applications than conventional formulations. In another embodiment, the composition further comprises an additional UV blocking agent.
In another embodiment, the composition further comprises a third phase. In further embodiment, the third phase comprises water. In another embodiment, the second phase comprises water and the water comes from the pest control agent. In an additional embodiment, the composition further comprises an emulsifier.
Example 1 (Oil emulsion carrier base for virus particles)
Add the Soprophor FLK (dispersing agent commercially available from Rhodia Novecare) into the water. Then, add the sunflower oil into the Soprophor/water mixture with high shear mixing. Measure the particle size after 30 seconds (it will approximately be 15-20μ). Measure again at 1 minute (the particle size will be approximately 8-12μ). Measure again after approximately 90 seconds (the particle size will be approximately 5-8μ with no flocculation). Laser-particle size analysis will show a
measurement of D10-2.371μ, D50-4.324μ, D90-7.715μ. Add a drop of anti-foam. After standing overnight, mix the composition with high shear mixing for at least two minutes and then add in 2g/L Rhodopol G (xanthan gum commercially available from Rhodia Novecare) and allow to disperse. Dilution of this composition in water will show fair bloom.
Example 2 (Pest control formulation with codling moth granulovirus)
Disperse virus concentrate into sunflower oil by high shear mixing. Then, dissolve Soprophor FLK , Tensiofix BCZ (sodium lauryl sulfate commercially available from omnichem) antifoam, and Rhodopol G into water. Next, add the oil / virus mixture into aqueous phase with high shear mixing. This forms a fluid, pale grey-brown composition which has some foam. The estimated particle size is an average of about 4- 6μ. The spontaneity of the dispersion is fair and upon dilution the composition turns pale gray with no foam. The Malvern laser particle size analysis result is:
Analysis ofpyrethrins HPLC chromatography is used to separate the pyrethrins. Butylparabene is selected as a standard and acetonitrile is used as solvent for the pyrethrins to prepare a solution for HPLC injection. Pyrethins I and π, jasmolin I and II are more suitable to monitor degradation than cinerin I and II because the degradation products ofpyrethrins I and II have some overlap with the peaks of the cinerins I and It. UV-radiation
A fluorescent tube (Philips Ultraviolet-B, TL40W/12RS) having an emission spectrum of 280-320 nm is used to provide UV-B light. The tube is placed in a dark room with a stable temperature of 22-24 °C. Open borosilicate 6 cm-diam. Petri dishes are placed on pre-indicated places under the UV-tube. The distance between the Petri dish and the underside of the UV-B tube is 14.5 cm. The level of irradiance is measured by a precalibrated spectroradiometer (Grόbel, Karlsruhe, Germany). The level is
2 "1
2.8 W/m or 0.29 mW/cm . To have an indication how this relates to the outdoor levels: irradiation level on a sunny day in Wageningen, Netherlands (04-04) at 14.00 h is 6.5
Z 2
W/m and the level on the next sunny day (05-04) on 16.20 h is 5 W/m . This means that the level in the test facility is about twice lower compared with the UV-B level on a sunny day in April in the Netherlands. Pyrethrin sample
The pyrethrin sample used in this test is Pyrethrum Extract Pale, which is a highly refined extract with 50% w/w total pyrethrins. The other 50% of the composition is described as "vegetable materials plus isoparaffm solvent."
RESULTS AND DISCUSSION
Tests for establishing protocol and exploiting some potential UV-protectants The internal standard butylparabene could be well analyzed in the same system and does not co-elute with any pyrethrin or their decomposition products. A substantial degradation of the pyrethrins can be measured during 3 h of UV-B irradiation (Fig. 1). The half-life time (DT50 value) in the test system is approximately 60 min. (Fig. 1) which is longer than the DT50 value of 10-12 min. reported for sunlight and equal to the value of approximately 75 min. measured with Pyrethrum Pale. The level of UV-B irradiation used
is about 2-fold lower than could be measured on a sunny day in Wageningen in April. Further, maximal absorbance of UV radiation may be in the 225 nm range which is not covered by the UV-B fluorescent tube. The 225 nm range may be present in natural sunlight. The reproducibility of the data is good: duplicate injections of the same samples give insignificant differences. Sunflower oil retards pyrethrin degradation (Fig. 2). In an embodiment, a pest control composition for application to a substrate comprises a pest control agent and a protective agent selected from a group consisting of: vegetable oil, modified vegetable oil, and derivatives of vegetable oil, wherein, in use, the pest control composition forms upon the substrate droplets or globules of the protective agent and the pest control agent is housed within or covered by the protective agent droplets or globules (or "igloos") to protect the pest control agent from environmental effects such as sunlight, oxidation and rain.
The composition may comprise an emulsion of the protective agent as a first phase within a second phase with the pest control agent being contained within the protective agent. As an example, a pest control agent such as codling moth granulovirus that is insoluble in the first phase may be dispersed as particulate matter within the first phase: In another example, a pest control agent such as codling moth granulovirus may be associated with a further agent such as sorbitan trioleate and then dispersed within the first phase so that the composition comprises droplets of the further agent containing the pest control agent and those droplets are dispersed within the first phase. In each of these examples, the pest control agent is provided within the droplets or globules of the first phase so that the first phase directly encapsulates or houses the pest control agent and protects it from environmental effects such as sunlight, oxidation and rain
As another example, the composition may comprise a liquid carrier carrying the pest control agent and the liquid carrier may be combined or mixed with protective agent to form an emulsion of protective agent within the liquid carrier such that, in use when applied to the substrate droplets or globules of protective agent coat or otherwise protect the pest control agent. As an example, a water-insoluble pest control agent such as pyrethrin plus synergist may be dissolved in a solvent (or a pest control agent such as carpovirusine may be dispersed in a liquid) and then combined or mixed with the protective agent and an emulsifier to form an emulsion of protective agent in water such that, in use, when the composition is applied to the substrate and dries as the solvent evaporates, droplets or globules of protective agent are left coating or otherwise protecting the pest control agent from environmental effects such as sunlight, oxidation and rain.
Any suitable form of vegetable oil or derivative may be used and the examples give herein should not be considered to represent an exhaustive list. Unsaturated, saturated and polyunsaturated vegetable oils may be used. Polyunsaturated vegetable oils have better UV blocking characteristics than unsaturated vegetable oils. As set out above a vegetable oil, modified vegetable oil or vegetable oil derivative is used. It may, however, be possible to use any biological oil ("bio-oil"), modified biological oil or biological oil derivative which is environmentally friendly, which is not significantly detrimental to the substrate to which the spray is to be applied, and which is palatable to the target of the pesticide. As used herein, a biological oil or "bio-oil" is an oil derived from or based on a biological source, such as a plant, vegetable, nut, seed, animal or fish. For example, it may be possible to use a fish oil, modified fish oil or fish oil derivative."
The specific illustrations and embodiments described herein are exemplary only in nature and are not intended to be limiting of the invention defined by the claims. Further embodiments and examples will be apparent to one of ordinary skill in the art in view of this specification and are within the scope of the claimed invention. What is claimed is:
Claims
1. A pest control composition for application to a substrate, the pest control composition comprising a pest control agent and a protective agent selected from a group consisting of: a biological oil, a modified biological oil, and a biological oil derivative, wherein, in use, the pest control composition forms upon the substrate droplets or globules of the protective agent and the pest control agent is housed within or covered by the protective agent droplets or globules.
2. A pest control composition according to claim 1, wherein the protective agent comprises a first phase and the composition further comprises a second phase.
3. A composition according to claim 2, wherein the second phase comprises water.
4. A composition according to claim 2 or 3, wherein the composition comprises an emulsion of the first phase in the second phase.
5. A composition according to claim 2 or 3, wherein the composition is a dispersion.
6. A composition according to claim 3 further comprising a third phase, wherein the third phase comprises water.
7. A composition according to claim 1, wherein the second phase comprises a second biological oil phase.
8. A composition according to claim 7, wherein the second biological oil phase is selected from the group consisting of: a biological oil, a modified biological oil, and a biological oil derivative; and the biological oil of the second biological oil phase is different from the biological oil in the first biological oil phase.
9. A composition according to claim 8, wherein the first and second biological oil phases form a dispersion of oil within oil.
10. A pest control composition according to claim 2, further comprising an emulsifier.
11. A composition according to claim 10, wherein the first biological oil phase comprises vegetable oil and the emulsifier comprises a derivative of vegetable oil.
12. A composition according to claim 11, wherein the first oil phase comprises sunflower oil and the emulsifier comprises sorbitan trioleate.
13. A composition according to claim 1, further comprising a diluent.
14. A composition according to claim 13, wherein the diluent comprises water.
15. A composition according to claim 14, wherein the composition comprises an emulsion.
16. A composition according to claim 1 wherein the composition comprises an emulsion of the protective agent as a first phase within a second phase and the pest control agent is contained within droplets or globules of the protective agent in the emulsion.
17. A composition according to claim 16, wherein the pest control agent is dispersed within the first phase.
18. A composition according to claim 16, wherein the pest control agent is provided within a further agent dispersed within the first phase.
19. A composition according to claim 18, wherein the further phase forms an further phase-in-first phase emulsion.
20. A composition according to claim 1, wherein the composition comprises a liquid carrier carrying the pest control agent and that the liquid carrier combines or mixes with the protective agent to form an emulsion of protective agent within the liquid carrier such that, in use, when applied to the substrate droplets or globules of protective agent coat or otherwise protect the pest control agent.
21. A composition according to any of the preceding claims, wherein the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, synthetic chemicals, and derivatives.
22. A composition according to claim 21, wherein the pest control agent is selected from the group consisting of: virus, fungus, bacteria, pyrethrin, and codling moth granulovirus.
23. A composition according to any of the preceding claims, wherein the or each biological oil, modified biological oil or biological oil derivative comprises at least one of: a fish oil, a modified fish oil; a fish oil derivative; a vegetable oil; a modified vegetable oil; and a vegetable oil derivative.
24. A composition according to any of claims 1 to 23,wherein the or each biological oil, modified biological oil or biological oil derivative is selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safflower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and modifications and derivatives thereof.
25. A composition according to claim 6, wherein the first biological oil phase comprises sunflower oil.
26. A composition according to claim 6, wherein the composition comprises a water- in-oil-in- water emulsion.
27. A composition according to claim 9, wherein the oil in the first biological oil phase comprises sorbitan trioleate.
28. A composition according to any of claims 1 to 6, wherein the biological oil comprises sunflower oil and the pest control agent comprises codling moth granulovirus.
29. A composition according to any of the preceding claims, further comprising a UV blocking agent.
30. A composition according to any of the preceding claims, wherein the composition is sprayable.
31. A method of providing a pest control composition for application to a substrate, the method comprising combining a pest control agent and a protective agent selected from a group consisting of: a biological oil, a modified biological oil, and a biological oil derivative so that, when the composition is applied to a substrate, the pest control composition forms upon the substrate droplets or globules of the protective agent and the pest control agent is housed within or covered by the protective agent droplets or globules.
32. A method according to claim 31, wherein the pest control agent is added to the to the protective agent which forms a first phase and the combination is added to a second phase.
33. A method according to claim 32, wherein the second phase comprises water.
34. A method according to claim 32, wherein the second phase comprises a second biological oil phase, wherein the second biological oil phase is selected from the group consisting of: a biological oil, a modified biological oil, and a biological oil derivative and the oil of the second biological oil phase is different from the oil in the first biological oil phase.
35. A method according to claim 33, further comprising a third phase, wherein the third phase comprises water.
36. A method according to claim 33, wherein the pest control agent contains residual water.
37. A method according to claim 31, wherein the protective agent comprises an biological oil phase and the method comprises: a) adding an emulsifier to the biological oil phase; b) adding the pest control agent with water; and c) adding the combination of (a) and (b) to water.
38. A method according to claim 37, wherein the oil phase comprises sunflower oil and the emulsifier comprises a vegetable oil derivative.
39. A method according to claim 38, wherein the emulsifier comprises sorbitan trioleate.
40. A method according to claim 32 or 33, wherein the composition further comprises a third phase.
41 A method according to claim 40, wherein the third phase comprises water.
42. A method according to claim 41, wherein the second phase comprises water and the water comes from the pest control agent.
43. A method according to any of claims 31 to 42, wherein the composition further comprises an emulsifier.
44. A method according to any of claims 31 to 43, wherein the pest control agent is selected from the group consisting of: environmentally sensitive agents, biological agents, natural products, modified natural products, synthetic chemicals, and derivatives.
45. A method according to claim 44, wherein the pest control agent is selected from the group consisting of: a virus, a fungus, a bacterium, pyrethrin, and codling moth granulovirus.
46. A method according to any of claims 31 to 45, wherein the or each biological oil, modified biological oil or biological oil derivative comprises at least one of: a fish oil, a modified fish oil; a fish oil derivative; a vegetable oil; a modified vegetable oil; and a vegetable oil derivative.
47. A method according to any of claims 31 to 45, wherein the or each biological oil, modified biological oil or biological oil derivative is selected from the group consisting of: cottonseed oil, peanut oil, coconut oil, corn oil, grape seed oil, sunflower oil, olive oil, safϊlower oil, canola oil, cashew oil, sesame oil, argan oil, soybean oil, rice bran oil and modifications and derivatives thereof.
48. A method according to any of claims 31 to 47, wherein the composition further comprises a UV blocking agent.
49. A method for applying a pest control composition, which method comprises spraying composition according to any of claims lto 30 or a composition provided by a method according to any of claims 31 to 48 onto a substrate.
50. A method according to claim 49, wherein the spraying uses electric field effect technology.
51. A method according to claim 49 or 50, wherein the spraying comprises ultra-low volume application.
52. A method according to claim 49, 50 or 51, wherein the composition is at a lower concentration than conventional formulations.
53. A method according to claim 49, 50 or 51, wherein the composition requires a lower number of applications than convention formulations.
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|---|---|---|---|
| US71843205P | 2005-09-19 | 2005-09-19 | |
| US60/718,432 | 2005-09-19 | ||
| US73143905P | 2005-10-28 | 2005-10-28 | |
| US60/731,439 | 2005-10-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015521584A (en) * | 2012-06-26 | 2015-07-30 | 住友化学株式会社 | Aqueous emulsion pesticide composition |
| JP2015525736A (en) * | 2012-06-26 | 2015-09-07 | 住友化学株式会社 | Aqueous emulsion pesticide composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003251B1 (en) * | 1977-12-20 | 1984-08-22 | Imperial Chemical Industries Plc | Insecticidal formulations and process for their preparation |
| IT1123122B (en) * | 1979-09-12 | 1986-04-30 | Montedison Spa | INSECTICIDE LIQUID COMPOSITIONS CONTAINING SYNTHETIC PYRETROIDS |
| IT1157914B (en) * | 1982-01-12 | 1987-02-18 | Montedison Spa | PYRETROID AND ESTERITIOPHOSPHORIC INSECTICIDE FORMULATIONS |
| FR2552627B1 (en) * | 1983-09-30 | 1985-12-06 | Rhone Poulenc Agrochimie | OIL PESTICIDE COMPOSITIONS BASED ON ENTOMOPATHOGENIC VIRUSES |
| JPS6137707A (en) * | 1984-07-31 | 1986-02-22 | Otsuka Chem Co Ltd | Agricultural oil-in-water type dispersible composition |
| EP0561990B1 (en) * | 1990-12-07 | 1998-10-07 | Temple University | Stabilized insect nematode compositions |
| US5958463A (en) * | 1991-07-29 | 1999-09-28 | Agri-Tek, Inc. | Agricultural pesticide formulations |
| FR2721800B1 (en) * | 1994-07-01 | 1997-12-26 | Roussel Uclaf | NEW EMULSIBLE CONCENTRATES CONTAINING SEVERAL PESTICIDES |
| DE19528529A1 (en) * | 1995-08-03 | 1997-02-06 | Bayer Ag | Pesticides |
| US5700473A (en) * | 1995-08-24 | 1997-12-23 | W. Neudorff Gmbh Kg | Triglyceride enhanced pyrethrin-based arthropodicidal composition |
| WO2002013608A1 (en) * | 2000-08-11 | 2002-02-21 | Virginia Tech Intellectual Properties, Inc. | Water soluble uv-protective coatings for biological pesticides and process for making same |
| US6767548B2 (en) * | 2002-02-15 | 2004-07-27 | Isp Investments Inc. | Gel inhibited liquid carrier for a biocide containing a carbodiimide and an emulsifier mixture |
| US7494662B2 (en) * | 2002-03-26 | 2009-02-24 | Kru Ltd. | Oil soluble photoprotective compounds and compositions from plant oil processing |
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| JP2015521584A (en) * | 2012-06-26 | 2015-07-30 | 住友化学株式会社 | Aqueous emulsion pesticide composition |
| JP2015525736A (en) * | 2012-06-26 | 2015-09-07 | 住友化学株式会社 | Aqueous emulsion pesticide composition |
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