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US20030008926A1 - Ant spray containing D-limonene and methods of making and using same - Google Patents

Ant spray containing D-limonene and methods of making and using same Download PDF

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Publication number
US20030008926A1
US20030008926A1 US10/235,450 US23545002A US2003008926A1 US 20030008926 A1 US20030008926 A1 US 20030008926A1 US 23545002 A US23545002 A US 23545002A US 2003008926 A1 US2003008926 A1 US 2003008926A1
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United States
Prior art keywords
weight
limonene
insecticidal composition
formulation
toxic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US10/235,450
Inventor
Tor McPartland
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Individual
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Individual
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Filing date
Publication date
Priority claimed from US09/706,158 external-priority patent/US6784211B1/en
Application filed by Individual filed Critical Individual
Priority to US10/235,450 priority Critical patent/US20030008926A1/en
Publication of US20030008926A1 publication Critical patent/US20030008926A1/en
Priority to PCT/US2003/025407 priority patent/WO2004021787A1/en
Priority to AU2003265430A priority patent/AU2003265430A1/en
Priority to CNA03820794XA priority patent/CN1678191A/en
Priority to BR0314327-9A priority patent/BR0314327A/en
Priority to CN2011101650906A priority patent/CN102318604A/en
Priority to MXPA05002548A priority patent/MXPA05002548A/en
Priority to CA2495826A priority patent/CA2495826C/en
Priority to JP2004534284A priority patent/JP2005538158A/en
Priority to US12/394,537 priority patent/US8133921B2/en
Abandoned legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/01Hydrocarbons
    • A61K31/015Hydrocarbons carbocyclic
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N27/00Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00Antiparasitic agents
    • A61P33/14Ectoparasiticides, e.g. scabicides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to an all-natural, food grade insecticidal composition that is effective in controlling insects including ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, mosquitoes, wood boring and eating insects, body and head lice and more particularly relates to an insecticidal composition that contains D-limonene, a nontoxic hydrophilic solvent, a non-toxic emulsifying agent, and a preservative, such that the insecticidal composition is an effective residual repellant and contact insecticide but is nontoxic to humans, household animals, and farm animals, and not harmful to landscaping, particularly rose bushes and ornamentals, indoor plants, foundations of structures, soil or the environment.
  • U.S. Pat. No. 4,379,168 to Dotolo discloses pesticides containing D-limonene as an insect-killing ingredient along with water-soluble surfactants or emulsifiers, and water.
  • the pesticide compositions are designed for use mainly as a dip to rid small animals of fleas and ticks and as a spray to kill fleas and ticks on small animals.
  • None of the compositions taught by Dotolo contain suitable amounts of emulsifying agent and D-limonene for the purpose of the present invention. None of the compositions taught by Dotolo contain any surfactants or emulsifiers that were selected for their safety.
  • the Kodak Laboratory Chemical Catalog No. 51 indicates that Triton X-100, which is disclosed as an acceptable emulsifier in Dotolo, is irritating to the skin and eyes.
  • U.S. Pat. No. 3,023,144 to Greathouse, et al. discloses germicides and fungicides containing about 25% by weight D-limonene, about 1% by weight of p-methyl acetophenone, and other unsaturated hydrocarbon cleavage products of D-limonene, up to about 7% by weight concentrated citrus oil foots and from 0.25% up to about 10% by weight salicylic acid.
  • the compositions are used for topical application on humans and animals to control infections of skin and external organs arising from wounds or from infestation by fungi, bacteria, and larvae.
  • the active ingredient for the biocidal activity of the compositions disclosed is not D-limonene but rather compounds such as p-methyl acetophenone, and other unsaturated hydrocarbon cleavage products of D-limonene.
  • insects such as ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf-eating beetles and caterpillars, cockroaches, flies, mosquitoes, wood boring and eating insects, wasps, body and head lice by repelling them, and which is non-toxic to humans, household animals, and house plants.
  • insects such as ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, spiders, earwigs, slugs and snails, cockroaches, flies, wasps, wood boring and eating insects, body and head lice by killing them, and which is non-toxic to humans, household animals, farm animals, house plants, and soil.
  • a food-grade insecticidal composition that includes an amount of D-limonene sufficient to provide insect control, a non-toxic hydrophilic solvent, and an amount of a non-toxic emulsifying agent sufficient to solubilize D-limonene in the solvent.
  • the inventive composition includes about 1% to about 20% by weight of D-limonene, about 1% to about 25% by weight of the selected non-toxic emulsifying agent, for example Alkamuls EL620, and about 98% to about 55% by weight of the selected non-toxic hydrophilic solvent.
  • the inventive composition also includes at least one food-grade preservative, such as sodium benzoate.
  • the non-toxic insecticidal compositions according to the present invention have a pleasant citrus scent and are suitable for use in any living environment.
  • the inventive compositions are made only from food-grade ingredients.
  • an ingredient or a composition is “food-grade” if it meets the U.S.F.D.A.'s G.R.A.S. (Generally Recognized as Safe) food grade standard.
  • the inventive compositions are made only from organic ingredients.
  • an ingredient or a composition is “organic” if it is made mainly of naturally occuring materials.
  • the inventive compositions are not only safe and non-toxic to humans, household animals such as dogs, cats, rabbits, birds, lizards, etc. and farm animals, but can also be used near food without any danger of contamination or accidental poisoning, and are safe even if ingested by humans or animals.
  • the inventive compositions will not harm landscaping foliage, indoor plants, soil, or foundations for structures.
  • the inventive compositions can also be applied in stalls and barns without harming animals in such structures. Since the inventive compositions are made of mainly naturally occurring materials, they are not harmful to the environment and do not cause any unwanted pollution. Thus, they can be applied to stalls, barns, and in the walls, roofs, and foundations of structures.
  • the inventive compositions can also be applied using yard and barn misting machines. They are also completely biodegradable.
  • D-limonene otherwise known as orange limonene or 1-methyl-4-(1 methylethenyl) cyclohexene or 4-isopropenyl-1-methyl cyclohexene, has a chemical formula of C 10 H 16 , a molecular weight of 136.2, and contains 88.1% C and 11.8% H by weight. It occurs in various ethereal oils, particularly in oils of lemon, orange, lime, grapefruit and bergamot. D-limonene can be cold pressed from citrus peels or obtained from steam extraction of citrus peels of orange, lemon, lime, grapefruit and bergamot. Some of the extractions can contain as high as 95% D-limonene.
  • the invention thus provides a valuable use for what would otherwise be a waste product. Distillation of the oils produces technical grades of D-limonene of higher purity, i.e., from about 95% to about 96%. D-limonene has a pleasant citrus scent. It can be suitably used in any living environment.
  • the D-form of limonene is a liquid having a boiling point of 175.5-176 degrees centigrade. It can be commercially obtained from Lykes Pasco Packing Company (Dade City, Fla.) or Florida Chemical Company (Lake Alfred, Fla.).
  • compositions of the present invention allow a user to provide insect control in interior and exterior settings.
  • Insect control can include repelling and/or killing insects, such that less insects are alive or present in a given area than if the compositions of the present invention had not been applied in the area.
  • the inventive compositions control a wide range of insects, including without limitations ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, mosquitoes, wood boring and eating insects, including termites, carpenter ants, and carpenter bees, and body lice and head lice.
  • D-limonene acts to soften the waxy coating on the exoskeleton of insects and thereby causes the softened coating to clog the external insect respiratory organs, known as spiracles.
  • the clogged spiracles interfere with the ability of the insect to obtain adequate amounts of oxygen, ultimately resulting in the death of the insect.
  • This invention is therefore also suitable against other pests, besides insects, which would be susceptible to the external effects set forth above.
  • the inventive compositions include a food-grade, non-toxic hydrophilic solvent.
  • Water is particularly preferred as the solvent as it is edible.
  • Other detoxic or nontoxic hydrophilic solvents for example, ethanol, dilute acetic acid solutions, hydrogen peroxide, and the like, can also be used.
  • Useful emulsifying agents include polyethoxylated castor oils.
  • One such emulsifying agent is available commercially under the trade name of Alkamuls EL620 from Rhone Poulenc Co. It is non-toxic to humans, household animals and house plants and landscaping and will not cause skin or eye irritation.
  • Castor oils also improve the insecticidal effect of the formulation. For example, the formulation of castor oil and D-limonene performs as an effective and enduring insect repellant. Castor oils also have the advantage of being an EPA “25b” active ingredient, thereby exempting it from registration as an active ingredient.
  • emulsifying agents that are nontoxic, such as polyoxyethylenesorbitans supplied by ICI Americas or Sigma Chemical Company, may also be suitably used for the present invention provided that they are foodgrade.
  • polyoxyethylenesorbitans supplied by ICI Americas or Sigma Chemical Company
  • a polyoxyethylenesorbitan monooleate such as Tween 80 may be used.
  • the emulsifying agent should be present in an amount sufficient to render the D-limonene soluble in the non-toxic hydrophilic solvent.
  • a polyethoxylated castor oil it should contain sufficient polyethoxylation to render the D-limonene soluble in a non-toxic hydrophilic solvent when the emulsifying agent is used in an amount as disclosed herein.
  • that solvent is water
  • the temperature of the water when combined with the other ingredients of the composition should be about 95° F. for optimal emulsification.
  • a preservative be added to the composition.
  • a preservative is sodium benzoate commercially supplied by Pfizer, Inc.
  • Preferred embodiments of the inventive insecticidal composition which are suitable for application as a spray, include about 0.7% to about 20% by weight, more preferably about 0.7% to about 10% by weight, of D-limonene, and even more preferably about 0.775% by weight D-limonene; between about 1% to about 25% by weight, more preferably about 5% to about 15% by weight, of a non-toxic emulsifying agent; about 0.01% to about 5% by weight, more preferably about 0.01% to about 1.0% by weight, of a preservative; and the balance of the selected solvent.
  • the inventive compositions are free of petroleum distillates.
  • novel insecticidal compositions When used indoors as a spray, they should be sprayed preferably from about 6 to about 8 inches away from and directly on insects such as ants, or on insect trails such as ant trails to the source of the insects such as ants (e.g., ant colonies, nests, etc.) and sprayed until visibly wet. Insects are typically killed within minutes of contact with the novel insecticidal compositions.
  • the insecticidal compositions can be used on the interior surfaces in a building such as counter tops and in food preparation areas.
  • the insecticidal compositions of the present invention should be applied at the perimeter of a building such as a home, at insect trails such as ant trails, at insect nests, such as ant nests and at doors, cracks, and window frames where insects such as ants may enter the building. It should be applied until visibly wet. It will provide lasting repellent qualities.
  • the insecticidal compositions can be used as a pretreatment for soils before construction and can be sprayed on and in walls, foundations, floors and roofs so that the composition is sealed or closed in during the construction process. This provides long-term repellence of wood boring and eating insects, including termites, carpenter ants, and carpenter bees.
  • the insecticidal compositions can also be pressure treated on wood, a quality useful in the construction industry.
  • the compositions are also a de-toxic alternative to arsenic for pressure treating studs, rafters, joists, and beams.
  • a composition having about 0.7% to about 20% by weight of D-limonene is combined with water, forming a treatment formulation.
  • a composition having about 0.7% to about 10% by weight D-limonene is combined with water.
  • a composition having about 5.8% by weight of D-limonene is combined with water.
  • Application of the present insecticidal compositions is preferably effected by spraying a treatment formulation of the insecticidal compositions by conventional spray apparatus such as aerosol can bug sprayers and the like.
  • the treatment formulation of the insecticidal compositions can be mixed with propellants or foaming agents to allow for various applications from an aerosol can.
  • Propellants that can be used include CFC, CO 2 , and nitrous oxide.
  • application may also be effected by any means of contacting surfaces to be treated, for example, with a brush which has been dipped in the treatment formulations of the insecticidal compositions. Because the novel insecticidal compositions are non-toxic, they can also be applied with a human hand.
  • the present invention When the present invention is applied to solid surfaces and left to remain there, the residual effect of the insecticidal composition will last for a period of time effectively keeping insects, such as ants, away from the treated area.
  • inventive insecticidal compositions can also be applied to a plant, such as a rose bush or other ornamental plant, in order to control insects.
  • inventive compositions can be formulated for use in treating humans, particularly children, infected with lice, particularly head lice.
  • novel insecticidal composition When used to treat humans infected with lice, it should be applied to the infected area, such as the scalp and left on for about 5 minutes after which it may be rinsed and preferably shampooed off.
  • the invention can be made as a concentrate that can be diluted with water.
  • the invention can be used as a paste and be effective in the control of head and body lice.
  • the treatment formulation of the insecticidal compositions can also be sprayed directly on humans and household animals to repel flying insects, in particular flies and mosquitoes.
  • a composition of the insecticide having about 0.7% to about 20% by weight, more preferably about 0.7% to about 10% by weight, and most preferably about 1.16% by weight, of D-limonene, is combined with water.
  • a preferred treatment batch is comprised of about six parts water to one part insecticidal composition, A more preferred treatment batch is about five parts water to about one part insecticidal composition, and a most preferred treatment batch is about four parts water to about one part insecticidal composition.
  • the treatment batch of the insecticidal compositions can also be used as a spray to be applied directly on farm animals to repel insects, in particular flying insects.
  • the treatment batch can also be used in stalls and barns to kill and repel flying and non-flying insects.
  • a treatment batch of the insecticide composition of the insecticide having about 0.7% to about 20% by weight, more preferably about 1.16% to about 10% by weight, and even more preferably about 1.6% by weight of D-limonene is used.
  • Batch treatments of the insecticidal compositions can also be used as a mosquito repellant for use in yard and barn misting machines and also for mosquito eradication and control for use in truck sprayers in infested areas such as an area infested with West Nile Virus.
  • the concentrated treatment of the insecticidal composition is diluted with water at a ratio of about six parts water to one part composition.
  • the concentrated treatment of the insecticidal composition is diluted with water at a ratio of about five parts water to one part composition to create a batch treatment and even more preferably at a ratio of three parts water to one part composition.
  • the batch treatments of the insecticidal composition can be used in fogging and misting machines for mosquitos, flies, and treating objects such as pallets.
  • the concentrated treatment of the insecticidal composition is diluted with water at a ratio from about one part insecticidal composition to three parts water, more preferably at a ratio from about one part insecticidal composition to about five parts water, and most preferably at a ratio of about one part composition to about six parts water.
  • the efficacy of the insecticidal composition can be increased by combining the composition with piperonyl butoxide (PBO).
  • PBO piperonyl butoxide
  • the insecticidal composition is combined with about 0.05% to about 0.2% PBO (piperonyl butoxide), more preferably with about 0.08% to about 0.15% PBO, and even more preferably with about 0.1% to about 0.12% PBO to increase the efficacy of the insecticidal composition.
  • the insecticidal composition according to the foregoing specific formulation has a white, opalescent color. Its physical state is a liquid at 25° C. and has a citrus-like odor. It has a boiling point between 99-100° C. and a specific gravity of 0.9753 gm/ml. It is soluble in water and has a pH of 6.1.
  • the flash point of the insecticidal composition is greater than 60° C. It has a viscosity of 1.97 centipoise at 37.8° C.
  • composition is diluted according to four parts water and one part stated composition for ornamentals and five parts water and one part stated composition for crops.

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Abstract

A food-grade insecticidal composition allowed for use in organic production which is effective in controlling insects, such as ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, mosquitoes, wood boring and eating insects, and body and head lice but which is non-toxic to humans, household animals, and farm animals includes an effective insect-controlling amount of D-limonene, a non-toxic emulsifying agent, and a non-toxic hydrophilic solvent.

Description

  • This is a continuation-in-part of U.S. patent application Ser. No. 09/706,158, filed Nov. 3, 2000, which is a continuation-in-part of U.S. patent application Ser. No. 09/218,732, filed Dec. 22, 1998, which is a continuation-in-part of U.S. patent application Ser. No. 08/846,351, filed Apr. 30, 1997, the disclosures of which are incorporated in their entirety herein by reference.[0001]
  • FIELD OF THE INVENTION
  • The present invention relates to an all-natural, food grade insecticidal composition that is effective in controlling insects including ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, mosquitoes, wood boring and eating insects, body and head lice and more particularly relates to an insecticidal composition that contains D-limonene, a nontoxic hydrophilic solvent, a non-toxic emulsifying agent, and a preservative, such that the insecticidal composition is an effective residual repellant and contact insecticide but is nontoxic to humans, household animals, and farm animals, and not harmful to landscaping, particularly rose bushes and ornamentals, indoor plants, foundations of structures, soil or the environment. [0002]
  • BACKGROUND OF THE INVENTION
  • Numerous pesticide and insecticide products are available in the market for killing insects such as ants. However, these products are generally toxic to humans and household animals, and harmful to plants and the environment. Therefore they must be administered with extreme care. This is especially a problem in the termination of ants, cockroaches and the like because they normally appear near food where a careless use of insecticides may cause accidental poisoning of humans and household animals. [0003]
  • Other insecticide products containing D-Limonene disperse the D-Limonene in mineral oil petroleum distillates which may be harmful if accidentally ingested and may cause damage to plants. No emulsifier is used because the D-Limonene is dispersed in oil and not water. [0004]
  • Lice infestation of humans, particularly children, is still treated with compositions that contain the pesticide lindane. Lindane is carcinogenic and an estrogen mimic. There exists a need for a composition which can treat body and head lice but which is safe to use, particularly on children. [0005]
  • U.S. Pat. No. 4,379,168 to Dotolo discloses pesticides containing D-limonene as an insect-killing ingredient along with water-soluble surfactants or emulsifiers, and water. The pesticide compositions are designed for use mainly as a dip to rid small animals of fleas and ticks and as a spray to kill fleas and ticks on small animals. None of the compositions taught by Dotolo contain suitable amounts of emulsifying agent and D-limonene for the purpose of the present invention. None of the compositions taught by Dotolo contain any surfactants or emulsifiers that were selected for their safety. For example, the Kodak Laboratory Chemical Catalog No. 51 indicates that Triton X-100, which is disclosed as an acceptable emulsifier in Dotolo, is irritating to the skin and eyes. [0006]
  • U.S. Pat. No. 3,023,144 to Greathouse, et al. discloses germicides and fungicides containing about 25% by weight D-limonene, about 1% by weight of p-methyl acetophenone, and other unsaturated hydrocarbon cleavage products of D-limonene, up to about 7% by weight concentrated citrus oil foots and from 0.25% up to about 10% by weight salicylic acid. The compositions are used for topical application on humans and animals to control infections of skin and external organs arising from wounds or from infestation by fungi, bacteria, and larvae. Greathouse discloses that the active ingredient for the biocidal activity of the compositions disclosed is not D-limonene but rather compounds such as p-methyl acetophenone, and other unsaturated hydrocarbon cleavage products of D-limonene. [0007]
  • A need exists for an insecticidal composition that kills on contact and controls insects such as ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf-eating beetles and caterpillars, cockroaches, flies, mosquitoes, wood boring and eating insects, wasps, body and head lice by repelling them, and which is non-toxic to humans, household animals, and house plants. [0008]
  • A need also exists for an insecticidal composition that is effective in controlling insects such as ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, spiders, earwigs, slugs and snails, cockroaches, flies, wasps, wood boring and eating insects, body and head lice by killing them, and which is non-toxic to humans, household animals, farm animals, house plants, and soil. [0009]
  • There is also a need for a safe and effective treatment for lice infestation of a human. [0010]
  • A need also exists for an insecticidal composition that contains an insecticide made from a natural substance that is part of and therefore not harmful to landscaping, particularly rose bushes and ornamentals, indoor plants or the environment. [0011]
  • A need also exists for an insecticidal composition that can be used around food, humans, household animals, and farm animals without worry. [0012]
  • There is also a need for an insecticidal composition that can be sprayed on humans and household animals that repels flying insects including flies and mosquitoes. There is also a need for an insecticidal composition that can be sprayed on farm animals and their living environment, including stalls and barns, that repels flying and non-flying insects. [0013]
  • There is also a need for a mosquito repellant for use in yard and barn misting machines and also for mosquito eradication and control for use in truck sprayers in infested areas, for example with West Nile Virus. [0014]
  • There is also a need for a pretreatment insect control that can be applied to soils and structures before construction, can be sprayed during construction on and in walls, foundations, floor and roof areas, and can be sealed or closed in during construction for long-term repellence of insects, including wood boring and eating insects, such as termites, carpenter ants, and carpenter bees. [0015]
  • A need also exists for a safe and effective insecticidal composition mixed with propellants or foaming agents to allow for various applications from an aerosol dispensers. [0016]
  • A need also exists for an insecticidal composition that can be emitted from a mosquito fogging or misting machine. [0017]
  • SUMMARY OF THE PREFERRED EMBODIMENTS
  • In accordance with one aspect of the present invention, there is provided a food-grade insecticidal composition that includes an amount of D-limonene sufficient to provide insect control, a non-toxic hydrophilic solvent, and an amount of a non-toxic emulsifying agent sufficient to solubilize D-limonene in the solvent. [0018]
  • Preferably, the inventive composition includes about 1% to about 20% by weight of D-limonene, about 1% to about 25% by weight of the selected non-toxic emulsifying agent, for example Alkamuls EL620, and about 98% to about 55% by weight of the selected non-toxic hydrophilic solvent. [0019]
  • In a preferred embodiment, the inventive composition also includes at least one food-grade preservative, such as sodium benzoate. [0020]
  • Methods of making and using the inventive compositions are also provided. [0021]
  • Other objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. It is to be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the present invention, are given by way of illustration and not limitation. Many changes and modifications within the scope of the present invention may be made without departing from the spirit thereof, and the invention includes all such modifications. [0022]
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The non-toxic insecticidal compositions according to the present invention have a pleasant citrus scent and are suitable for use in any living environment. In particular, the inventive compositions are made only from food-grade ingredients. As used herein, an ingredient or a composition is “food-grade” if it meets the U.S.F.D.A.'s G.R.A.S. (Generally Recognized as Safe) food grade standard. Additionally, in a preferred embodiment of the invention, the inventive compositions are made only from organic ingredients. As used herein, an ingredient or a composition is “organic” if it is made mainly of naturally occuring materials. Thus, the inventive compositions are not only safe and non-toxic to humans, household animals such as dogs, cats, rabbits, birds, lizards, etc. and farm animals, but can also be used near food without any danger of contamination or accidental poisoning, and are safe even if ingested by humans or animals. The inventive compositions will not harm landscaping foliage, indoor plants, soil, or foundations for structures. The inventive compositions can also be applied in stalls and barns without harming animals in such structures. Since the inventive compositions are made of mainly naturally occurring materials, they are not harmful to the environment and do not cause any unwanted pollution. Thus, they can be applied to stalls, barns, and in the walls, roofs, and foundations of structures. The inventive compositions can also be applied using yard and barn misting machines. They are also completely biodegradable. [0023]
  • D-limonene, otherwise known as orange limonene or 1-methyl-4-(1 methylethenyl) cyclohexene or 4-isopropenyl-1-methyl cyclohexene, has a chemical formula of C[0024] 10H16, a molecular weight of 136.2, and contains 88.1% C and 11.8% H by weight. It occurs in various ethereal oils, particularly in oils of lemon, orange, lime, grapefruit and bergamot. D-limonene can be cold pressed from citrus peels or obtained from steam extraction of citrus peels of orange, lemon, lime, grapefruit and bergamot. Some of the extractions can contain as high as 95% D-limonene. The invention thus provides a valuable use for what would otherwise be a waste product. Distillation of the oils produces technical grades of D-limonene of higher purity, i.e., from about 95% to about 96%. D-limonene has a pleasant citrus scent. It can be suitably used in any living environment.
  • The D-form of limonene is a liquid having a boiling point of 175.5-176 degrees centigrade. It can be commercially obtained from Lykes Pasco Packing Company (Dade City, Fla.) or Florida Chemical Company (Lake Alfred, Fla.). [0025]
  • The compositions of the present invention allow a user to provide insect control in interior and exterior settings. Insect control can include repelling and/or killing insects, such that less insects are alive or present in a given area than if the compositions of the present invention had not been applied in the area. The inventive compositions control a wide range of insects, including without limitations ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, mosquitoes, wood boring and eating insects, including termites, carpenter ants, and carpenter bees, and body lice and head lice. [0026]
  • While not limiting the invention by any particular theory, it is believed that the D-limonene acts to soften the waxy coating on the exoskeleton of insects and thereby causes the softened coating to clog the external insect respiratory organs, known as spiracles. The clogged spiracles interfere with the ability of the insect to obtain adequate amounts of oxygen, ultimately resulting in the death of the insect. This invention is therefore also suitable against other pests, besides insects, which would be susceptible to the external effects set forth above. [0027]
  • The inventive compositions include a food-grade, non-toxic hydrophilic solvent. Water is particularly preferred as the solvent as it is edible. Other detoxic or nontoxic hydrophilic solvents, for example, ethanol, dilute acetic acid solutions, hydrogen peroxide, and the like, can also be used. [0028]
  • Useful emulsifying agents include polyethoxylated castor oils. One such emulsifying agent is available commercially under the trade name of Alkamuls EL620 from Rhone Poulenc Co. It is non-toxic to humans, household animals and house plants and landscaping and will not cause skin or eye irritation. Castor oils also improve the insecticidal effect of the formulation. For example, the formulation of castor oil and D-limonene performs as an effective and enduring insect repellant. Castor oils also have the advantage of being an EPA “25b” active ingredient, thereby exempting it from registration as an active ingredient. Other commercially available emulsifying agents that are nontoxic, such as polyoxyethylenesorbitans supplied by ICI Americas or Sigma Chemical Company, may also be suitably used for the present invention provided that they are foodgrade. In a preferred embodiment a polyoxyethylenesorbitan monooleate such as Tween 80 may be used. [0029]
  • In general, the emulsifying agent should be present in an amount sufficient to render the D-limonene soluble in the non-toxic hydrophilic solvent. When a polyethoxylated castor oil is used, it should contain sufficient polyethoxylation to render the D-limonene soluble in a non-toxic hydrophilic solvent when the emulsifying agent is used in an amount as disclosed herein. When that solvent is water, the temperature of the water when combined with the other ingredients of the composition should be about 95° F. for optimal emulsification. [0030]
  • In order to provide a reasonable shelf-life to the insecticidal compositions, it is preferable that a preservative be added to the composition. One such suitable preservative is sodium benzoate commercially supplied by Pfizer, Inc. Other commercially available preservatives used for preserving food, as would be known to those of ordinary skill in the art, may also be suitably used. [0031]
  • Preferred embodiments of the inventive insecticidal composition, which are suitable for application as a spray, include about 0.7% to about 20% by weight, more preferably about 0.7% to about 10% by weight, of D-limonene, and even more preferably about 0.775% by weight D-limonene; between about 1% to about 25% by weight, more preferably about 5% to about 15% by weight, of a non-toxic emulsifying agent; about 0.01% to about 5% by weight, more preferably about 0.01% to about 1.0% by weight, of a preservative; and the balance of the selected solvent. [0032]
  • Preferably, the inventive compositions are free of petroleum distillates. [0033]
  • When the novel insecticidal compositions are used indoors as a spray, they should be sprayed preferably from about [0034] 6 to about 8 inches away from and directly on insects such as ants, or on insect trails such as ant trails to the source of the insects such as ants (e.g., ant colonies, nests, etc.) and sprayed until visibly wet. Insects are typically killed within minutes of contact with the novel insecticidal compositions.
  • The insecticidal compositions can be used on the interior surfaces in a building such as counter tops and in food preparation areas. For outdoor use, the insecticidal compositions of the present invention should be applied at the perimeter of a building such as a home, at insect trails such as ant trails, at insect nests, such as ant nests and at doors, cracks, and window frames where insects such as ants may enter the building. It should be applied until visibly wet. It will provide lasting repellent qualities. [0035]
  • The insecticidal compositions can be used as a pretreatment for soils before construction and can be sprayed on and in walls, foundations, floors and roofs so that the composition is sealed or closed in during the construction process. This provides long-term repellence of wood boring and eating insects, including termites, carpenter ants, and carpenter bees. The insecticidal compositions can also be pressure treated on wood, a quality useful in the construction industry. The compositions are also a de-toxic alternative to arsenic for pressure treating studs, rafters, joists, and beams. [0036]
  • In a preferred embodiment, a composition having about 0.7% to about 20% by weight of D-limonene is combined with water, forming a treatment formulation. In a more preferred embodiment, a composition having about 0.7% to about 10% by weight D-limonene is combined with water. In a most preferred embodiment, a composition having about 5.8% by weight of D-limonene is combined with water. [0037]
  • Application of the present insecticidal compositions is preferably effected by spraying a treatment formulation of the insecticidal compositions by conventional spray apparatus such as aerosol can bug sprayers and the like. The treatment formulation of the insecticidal compositions can be mixed with propellants or foaming agents to allow for various applications from an aerosol can. Propellants that can be used include CFC, CO[0038] 2, and nitrous oxide. However, application may also be effected by any means of contacting surfaces to be treated, for example, with a brush which has been dipped in the treatment formulations of the insecticidal compositions. Because the novel insecticidal compositions are non-toxic, they can also be applied with a human hand.
  • When the present invention is applied to solid surfaces and left to remain there, the residual effect of the insecticidal composition will last for a period of time effectively keeping insects, such as ants, away from the treated area. [0039]
  • The inventive insecticidal compositions can also be applied to a plant, such as a rose bush or other ornamental plant, in order to control insects. [0040]
  • Further embodiments of the inventive compositions can be formulated for use in treating humans, particularly children, infected with lice, particularly head lice. When the novel insecticidal composition is used to treat humans infected with lice, it should be applied to the infected area, such as the scalp and left on for about 5 minutes after which it may be rinsed and preferably shampooed off. [0041]
  • The invention can be made as a concentrate that can be diluted with water. The invention can be used as a paste and be effective in the control of head and body lice. [0042]
  • The treatment formulation of the insecticidal compositions can also be sprayed directly on humans and household animals to repel flying insects, in particular flies and mosquitoes. In a preferred embodiment, a composition of the insecticide having about 0.7% to about 20% by weight, more preferably about 0.7% to about 10% by weight, and most preferably about 1.16% by weight, of D-limonene, is combined with water. A preferred treatment batch is comprised of about six parts water to one part insecticidal composition, A more preferred treatment batch is about five parts water to about one part insecticidal composition, and a most preferred treatment batch is about four parts water to about one part insecticidal composition. [0043]
  • The treatment batch of the insecticidal compositions can also be used as a spray to be applied directly on farm animals to repel insects, in particular flying insects. The treatment batch can also be used in stalls and barns to kill and repel flying and non-flying insects. Preferably, a treatment batch of the insecticide composition of the insecticide having about 0.7% to about 20% by weight, more preferably about 1.16% to about 10% by weight, and even more preferably about 1.6% by weight of D-limonene is used. [0044]
  • Batch treatments of the insecticidal compositions can also be used as a mosquito repellant for use in yard and barn misting machines and also for mosquito eradication and control for use in truck sprayers in infested areas such as an area infested with West Nile Virus. In a preferred embodiment, the concentrated treatment of the insecticidal composition is diluted with water at a ratio of about six parts water to one part composition. In a more preferred embodiment, the concentrated treatment of the insecticidal composition is diluted with water at a ratio of about five parts water to one part composition to create a batch treatment and even more preferably at a ratio of three parts water to one part composition. [0045]
  • The batch treatments of the insecticidal composition can be used in fogging and misting machines for mosquitos, flies, and treating objects such as pallets. In a preferred embodiment the concentrated treatment of the insecticidal composition is diluted with water at a ratio from about one part insecticidal composition to three parts water, more preferably at a ratio from about one part insecticidal composition to about five parts water, and most preferably at a ratio of about one part composition to about six parts water. [0046]
  • The efficacy of the insecticidal composition can be increased by combining the composition with piperonyl butoxide (PBO). In a preferred embodiment, the insecticidal composition is combined with about 0.05% to about 0.2% PBO (piperonyl butoxide), more preferably with about 0.08% to about 0.15% PBO, and even more preferably with about 0.1% to about 0.12% PBO to increase the efficacy of the insecticidal composition. [0047]
  • Non-limiting examples of the inventive insecticidal composition are set forth below.[0048]
  • EXAMPLE 1
  • For home, office, school, institutional or industrial applications, indoor and outdoor (proven effective against ants, roaches and fleas but is a broad based insecticide and repellent): [0049]
  • 6 wt % D-limonene (0.2% impurities in the D-limonene, net active 5.8%) [0050]
  • 10 wt % Alkamuls EL620 (polyethoxylated caster oil) [0051]
  • 0.1 wt % sodium benzoate [0052]
  • 83.9 wt % water. [0053]
  • The insecticidal composition according to the foregoing specific formulation has a white, opalescent color. Its physical state is a liquid at 25° C. and has a citrus-like odor. It has a boiling point between 99-100° C. and a specific gravity of 0.9753 gm/ml. It is soluble in water and has a pH of 6.1. The flash point of the insecticidal composition is greater than 60° C. It has a viscosity of 1.97 centipoise at 37.8° C. [0054]
  • EXAMPLE 2
  • For agriculture, on food and ornamental crops (proven effective on aphids and spider mites but useful for many other plant pests): [0055]
  • 0.967% to 1.16% D-limonene (0.05% impurities in the d-Limonene, net active 0.725%) [0056]
  • 1.667% to 2.8% Alkamuls EL 620 [0057]
  • 0.025% Sodium Benzoate [0058]
  • 95.975% Water (UV sterilized and particulate filtered to 5 microns) or dionized; [0059]
  • The foregoing composition is diluted according to four parts water and one part stated composition for ornamentals and five parts water and one part stated composition for crops. [0060]
  • EXAMPLE 3
  • As a liquid concentrate to make the two previous formulations by simply adding the proper ratio of warm [0061] 95° F. water:
  • 18% D-limonene (0.6% impurities in the D-limonene, net active 17.4%) [0062]
  • 30% Alkamuls EL 620 [0063]
  • 0.3% Sodium Benzoate [0064]
  • 51.7% Water (UV sterilized and particulate filtered to 5 microns) or dionized [0065]
  • EXAMPLE 4
  • As a paste for applying to head and body as a treatment for lice (puts lice into a state of morbidity making for easy removal): [0066]
  • 24% D-limonene (0.8% impurities in the D-limonene, net active 23.2%) [0067]
  • 40% Alkamuls EL 620 [0068]
  • 0.1% Sodium Benzoate [0069]
  • 35.9% Water (UV sterilized and particulate filtered to 5 microns) or dionized [0070]
  • EXAMPLE 5
  • As a spray that is ready to use for spraying directly on humans, household animals, and on plants for repelling flying insects including flies and mosquitoes [0071]
  • 1.2% D-limonene (0.04% impurities in the D-limonene, net active 1.16%) [0072]
  • 2.0% Alkamuls [0073]
  • 0.1% Sodium Benzoate [0074]
  • 96.7% Water (UV sterilized and particulate filtered to 5 microns) or dionized. [0075]
  • EXAMPLE 6
  • As a spray for spraying directly on farm animals for repelling insects, including flying insects, and in farm animal living areas for repelling flying and non-flying insects: [0076]
  • 1.5% D-limonene (0.05% impurities in the D-limonene, net active 1.45%) [0077]
  • 98.4% Water (UV sterilized and particulate filtered to 5 microns) or dionized. [0078]
  • EXAMPLE 7
  • As a pretreatment for a structure, foundation, or soil before construction for repelling wood boring and eating insects: [0079]
  • 6.0% d-limonene (0.2% impurities in the d-limonene, net active 5.8%) [0080]
  • 10% emulsifying agent [0081]
  • 83.9% water (UV sterilized and particulate filtered to 5 microns) or dionized. [0082]
  • 0.1% sodium benzoate [0083]

Claims (48)

What is claimed is:
1. A food-grade insecticidal composition comprising an amount of D-limonene sufficient to provide insect control, a de-toxic hydrophilic solvent, an amount of a non-toxic emulsifying agent sufficient to solubilize D-limonene in said de-toxic hydrophilic solvent, wherein the emulsifying agent is de-toxic to humans.
2. The insecticidal composition according to claim 1 comprising about 1% to about 20% by weight of D-limonene, about 1% to about 25% by weight said detoxic emulsifying agent, and about 98% to about 55% by weight of said de-toxic hydrophilic solvent.
3. The insecticidal composition according to claim 1 further comprising an amount of at least one food-grade preservative sufficient to extend the effectiveness of said insecticidal composition.
4. The insecticidal composition according to claim 3 comprising about 0.01% to about 5% by weight of said preservative.
5. The insecticidal composition according to claim 1 wherein said amount of D-limonene sufficient to provide insect control is sufficient to repel an insect.
6. The insecticidal composition according to claim 1 wherein said amount of D-limonene sufficient to provide insect control is sufficient to kill an insect.
7. The insecticidal composition according to claim 1 wherein said nontoxic emulsifying agent is a polyethoxylated castor oil.
8. The insecticidal composition according to claim 1 wherein said detoxic emulsifying agent is a polyoxyethylenesorbitan.
9. The insecticidal composition according to claim 1 wherein said detoxic hydrophilic solvent is water.
10. The insecticidal composition according to claim 2 wherein said preservative is a food preservative.
11. The insecticidal composition according to claim 1 which controls at least one insect selected from the group consisting of ants, aphids, mealy bugs, white flies, spider mites, leaf hoppers, cabbage loopers, leaf eating beetles and caterpillars, cockroaches, flies, wasps, body lice and head lice.
12. The insecticidal composition according to claim 1 comprising about 1% to about 10% by weight of D-limonene, about 5% to about 15% by weight of a non-toxic emulsifying agent, and about 94% to about 75% by weight of a non-toxic hydrophilic solvent.
13. The insecticidal composition according to claim 1 wherein said composition is suitable for organic production.
14. The insecticidal composition according to claim 2 wherein said nontoxic emulsifying agent is castor oil.
15. A method of making an insecticidal composition comprising the step of combining an amount of D-limonene sufficient to provide insect control with a de-toxic hydrophilic solvent and an amount of a de-toxic emulsifying agent sufficient to solubilize D-limonene in said de-toxic hydrophilic solvent, wherein all said ingredients are food-grade.
16. The method of claim 15 comprising the step of combining about 1% to about 20% by weight of D-limonene, about 1% to about 25% by weight of said non-toxic emulsifying agent and about 97.99% to about 50% by weight of said non-toxic hydrophilic solvent.
17. The method of claim 16 wherein said solvent is water.
18. The method of claim 16 wherein said ingredients are combined with about 0.01% to about 5% by weight of a preservative.
19. A method as recited in claim 16 wherein said insecticidal composition is used in organic production.
20. A method of controlling insects comprising the step of applying the insecticidal composition of claim 1 to one selected from the group consisting of an insect, an insect trail, an insect nest, a building surface, a building perimeter, and a plant.
21. The method of claim 20 wherein said insects to be controlled are on plants.
22. The method of claim 21 wherein said plants are selected from the group consisting of rose bushes and ornamentals.
23. A method of repelling insects comprising the step of pressure treating wood with the insecticidal composition of claim 1.
24. A method as recited in claim 23 further comprising pressure treating studs, rafters, joists, and beams.
25. A method of treating a human infected with lice comprising the steps of applying the composition of claim 1 to a portion of the human infected with the lice, allowing said composition to remain on the infected portion for a period of time and removing said composition.
26. A food-grade insecticidal composition comprising about 0.7% to about 1.5% by weight of D-limonene, about 1% to about 25% by weight of a castor oil and about 98% to about 55% by weight of a non-toxic hydrophilic solvent.
27. The insecticidal composition according to claim 26 further comprising an amount of at least one food-grade preservative sufficient to extend the effectiveness of the insecticidal composition.
28. The insecticidal composition according to claim 27 comprising about 0.01% to about 5% by weight of said preservative.
29. The insecticidal composition according to claim 27 comprising about 0.775% D-limonene.
30. A method of eradicating fire ants, comprising:
applying a formulation to an area to be eradicated of fire ants, wherein said formulation consists essentially of about 0.7% to about 1.5% D-limonene, about 1% to about 25% by weight of an emulsifying agent, and about 98% to about 55% by weight of a non-toxic hydrophilic solvent; and
allowing said formulation to remain in contact with said area for a suitable period of time to eradicate said fire ants.
31. A method of eradicating fire ants, comprising:
applying a formulation to an area to be eradicated of fire ants, wherein said formulation consists essentially of about 1.5% to about 6% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a non-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative; and
allowing said formulation to remain in contact with said area for a suitable period of time to eradicate said fire ants.
32. A method of repelling insects from a farm animal comprising:
applying a treatment batch on the farm animals comprising four parts water to one part formulation, wherein said formulation consists essentially of about 1.16% to about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a non-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative.
33. A method of repelling insects from a farm animal comprising:
applying a treatment batch on the farm animals comprising six parts water to one part formulation, wherein said formulation consists essentially of about 1.1 6% to about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a non-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative.
34 A method of repelling insects from a farm animal comprising:
applying a treatment batch on the farm animals comprising ten parts water to one part formulation, wherein said formulation consists essentially of about 1.16% to about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a non-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative.
35. A method of pretreating a structure and foundation before construction to repel wood boring and eating insects comprising:
applying a formulation on the structure and foundation, wherein the formulation consists of about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, and about 98% to about 55% by weight of a non-toxic hydrophilic solvent.
36. A method of using an insecticidal composition in a fogging machine comprising:
an insecticidal composition consisting of about 1.16% to about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a de-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative; and
supplying the fogging machine with the insecticidal composition.
37. A method as recited in claim 36 wherein the fogging machine is a yard and barn misting machine.
38. A method as recited in claim 36 wherein the insecticidal composition is used as a treatment for mosquitos and flies and for pallets within an enclosed area.
39. A method of increasing the efficacy of an insecticidal composition comprising:
diluting the insecticidal composition with about 0.05% to about 0.2% of a PBO, wherein the insecticidal composition consists of about 1.16% to about 5.8% D-limonene, about 1% to about 25% by weight of an emulsifying agent, about 98% to about 55% by weight of a de-toxic hydrophilic solvent, and about 0.01% to about 5% by weight of a food-grade preservative; and
supplying the fogging machine with the diluted insecticidal composition.
40. A method of increasing the efficacy of an insecticidal composition comprising:
diluting the insecticidal composition with about 0.5% to about 5% sesame oil, wherein the insecticidal composition consists of about 1.16% to 5.8% D-limonene, about 6% to 10% castor oil, and 0.025% to 0.1% food-grade antioxidant preservative; and
supplying a fogging machine with the diluted insecticidal composition.
41. A method of repelling insects from a human comprising:
applying a formulation on the human, wherein said formulation consists of about 0.7% to about 20% D-limonene; and
combining the formulation with water, wherein six parts water is combined with one part formulation.
42. A method as recited in claim 41 wherein the formulation consists of about 0.7% to about 10% D-limonene and wherein five parts water is combined with one part formulation.
43. A method as recited in claim 41 wherein the formulation consists of about 1.16% D-limonene and wherein four parts water is combined with one part formulation.
44. A method as recited in claim 41 wherein applying a formulation further includes spraying the formulation on the human.
45. A method of repelling insects from a household animal comprising:
applying a formulation on the household animal, wherein said formulation consists of about 0.7% to about 20% D-limonene; and
combining the formulation with water, wherein six parts water is combined with one part formulation.
46. A method as recited in claim 45 wherein the formulation consists of about 0.7% to about 10% D-limonene and wherein five parts water is combined with one part formulation.
47. A method as recited in claim 45 wherein the formulation consists of about 1.16% D-limonene and wherein four parts water is combined with one part formulation.
48. A method as recited in claim 45 wherein applying a formulation further includes spraying the formulation on the household animal.
US10/235,450 1997-04-30 2002-09-04 Ant spray containing D-limonene and methods of making and using same Abandoned US20030008926A1 (en)

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CA2495826A CA2495826C (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene and methods of making and using same
CNA03820794XA CN1678191A (en) 2002-09-04 2003-08-13 Ant spray containing D-limonene
AU2003265430A AU2003265430A1 (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene
PCT/US2003/025407 WO2004021787A1 (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene
BR0314327-9A BR0314327A (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene and methods of preparing and using it
CN2011101650906A CN102318604A (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene
MXPA05002548A MXPA05002548A (en) 2002-09-04 2003-08-13 Ant spray containing d-limonene.
US12/394,537 US8133921B2 (en) 1997-04-30 2009-02-27 Edible plant extract based insecticidal composition

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US8133921B2 (en) 2012-03-13
AU2003265430A1 (en) 2004-03-29

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