WO2000005948A1

WO2000005948A1 - Vapor releasable, geraniols containing, tick and insect repellent compositions and methods

Info

Publication number: WO2000005948A1
Application number: PCT/US1999/000997
Authority: WO
Inventors: Carl J. Abraham
Original assignee: Abraham Carl J
Priority date: 1998-07-27
Filing date: 1999-01-19
Publication date: 2000-02-10
Also published as: AU2458599A

Abstract

An insect repellent including a liquid system containing Geraniol and a fragrance oil which acts as a carrier for dispersing Geraniol vapor into the atmosphere upon evaporation of the fragrance oil. In one embodiment of the invention, the liquid system is contained within a solid thermoplastic system which can be formed as pellets for fabricating utilitarian products, e.g., wristbands and tablecloths. In another embodiment of the invention, the liquid system is contained within the wax of a candle which can be burned to emit Geraniol vapor into the atmosphere. In a third embodiment, the liquid system can be mixed with alcohol, with or without water, and dispersed by an air-wick or fan to repel insects and ticks. In a fourth embodiment, towelettes can be soaked in the liquid system for later use as applicators of the liquid system to areas of the skin of humans and animals from which Geraniol vapor can be released into the atmosphere for effectively repelling insects and ticks from around the entire body.

Description

VAPOR RELEASABLE, GERANIOLS CONTAINING, ΗCK AND INSECT REPELLENT COMPOSITIONS AND METHODS.

Background of the Invention This invention relates to tick, red fire ant and insect repellents based on Geraniol mixtures and compounds. More specifically, the invention is directed to the incorporation of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG into a solid or liquid medium from which the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, can vaporize at ambient temperatures at a rate sufficient to repel insects. The invention also teaches the incorporation of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG into a candle, from which the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, can vaporize when lit.

Ticks are known to be carriers of disease, particularly ly e disease, a serious debilitating illness. Various prior art products which seek to repel ticks from human beings have met with little success. DEET (N, N-diethyl-m-toluamide) a material used in many insect repellents, is of limited effectiveness against insects and fire ants, and of no significant effectiveness in repelling ticks. Moreover only those areas of the body to which the DEET has been topically applied are partially protected from insect bites. It is known to use Citronella, and/or DEET in the prior art to repel insects from a surface by depositing Citronella, and/or DEET on the surface. Ticks are contact anthropods that attach themselves to a human through contact with their clothing after brushing against a bush, tall grass or an animal such as a dog. In order to eliminate or minimize that possibility, prior art insecticides which are highly toxic are sprayed only on clothing. Because of their toxicity they may not be applied to the skin.

It has recently been learned that Geraniol can be an effective insect repellent. See for example, U.S. Patents Nos. 5,633,236, 5,635,173 and 5,665,781 to Warren et al, European Patent No. 0660667 to Warren et al., and U.S. Patent No. 5,753,686 to Marin et al . However, prior to the instant invention, the use of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG to repel ticks and as a vapor to repel insects, without requiring contact of the ticks and insects with a surface to which the repellent had been applied was unknown.

As disclosed in my U.S. Patent No. 5,738,862, DEET can be vaporized with the aid of a fragrance to repel insects before they land on a person. However, DEET is also of limited effectiveness against ticks. DEET cannot be used under clothing. It is effective only on exposed skin. It is also known in the prior art to encapsulate insect repellents in time control release agents. Examples of such repellent systems are disclosed in U.S. Patent No. 4,548,764 to Munteanu et al. and U.S. Patent No. 5,069,231 to Rutherford. Prior art repellent encapsulation systems have a very limited life and are typically effective for less than one week. Such prior art systems are also very complex in that they require lactone groups and hydroxyl groups, and/or polyurethane in the repellent medium. Others call for polyoxyalkylene diols, linear polyster diols, and the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids. Still others require poly(epsilon caprolactone) as a cross linking agent for polyurethane. Highly volatile materials such as esthers, ethers, and aldehydes are commonly found in prior art compositions. Such prior art compositions are inherently unstable and therefore require stabilizers.

My U.S. Patent No. 5,738,862 describes a formulation for releasing DEET into the atmosphere to repel flying insects, including a molded system created without encapsulation that results in the slow vaporization of a relatively non-volatile liquid into the air to repel insects. However, DEET has been found to have limited effectiveness in repelling anthropods such as ticks.

Summary of the Invention

The aforementioned problems of the prior art are overcome by the instant invention which provides for the incorporation of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG an a fragrance oil into a solid thermoplastic material such as polyethylene or polystyrene or a liquid medium such as alcohol or a mixture of water and alcohol to form an effective system for repelling insects through the emission of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor therefrom and its dispersion into the atmosphere at ambient temperatures. The invention, for the first time, enables the use of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor as an insect repellent through the use of fragrances containing middle and low note ingredients that, during molding into products, retain large amounts of residual ingredients at short term exposures to 170°F to 195°F. The Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG formulation may also be applied by dabbing a towelette containing the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG solution of the invention onto limited areas of the body, e.g., the wrists and elbows. Because the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG is dispersed into the surrounding air, such applications are effective in repelling insects before they reach the body thereby rendering the entire body protected. The Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, when applied to the skin and under one's clothing, also prevents ticks from penetrating clothing and coming in contact with the proximate skin.

The invention further provides for the incorporation of a mixture of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and a fragrance oil into the wax of a candle. When the candle is lit, the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG withstands the heat of the candle and is carried into the atmosphere with the vaporized fragrance oil and candle wax to form an effective system for repelling insects through the emission of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor therefrom and its dispersion into the atmosphere.

Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, with or without fragranced oil, can also be sprayed into the air, e.g., inside a barn, to repel flying insects. The addition of fragranced oil enhances the spread and effectiveness of the active ingredient, i.e., Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG .

It is therefore an object of the invention to provide a tick, fire ant, and insect repellent medium from which

Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor can be dispersed at ambient temperatures to repel insects .

7Λnother object of the invention is to provide an insect repellent medium from which Geraniol, Geraniol Coeur, Geraniol

CFT, and/or Geraniol RG vapor can be dispersed from a solid or liquid medium over a period of time on the order of a month or more.

Still another object of the invention is to provide a repellent medium which is effective in repelling ticks, red fire ants, and insects yet non-toxic to humans and animals.

A further object of the invention is to provide an insect repellent medium from which utilitarian products such as wrist bands and ankle bands can be fabricated. Still a further object of the invention is to provide a method of dispersing a repellent medium into the atmosphere for repelling ticks and insects. Other and further objects of the invention will be apparent from the following description of a preferred embodiment of the invention.

Description of the Preferred Embodiment The present invention employs a mixture of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and a volatile fragrance oil having residual ingredients that are retentive, preferably in the range of 170°F - 195°F. Geraniol Coeur (3,7 dimethyl-2, 6-octadien-l-ol ) contains Geraniol, Citronella, and Nerol in the proportions: Geraniol 50o-75o (all percentages herein being by weight), Citronella 20?>-357^',, and Nerol 57,-20?,, by weight. Geraniol CFT (3,7 dimethyl-2, 6- octadien-1-ol or 2,6 dimethyl-2, 6-octadien-8-ol ) contains Geraniol and Nerol in the proportions: Geraniol 707,-95?,, Nerol up to 12", by weight. Geraniol RG (3,7 dimethyl-2, 6-octadien- l-ol) contains Geraniol and Nerol in the proportions: Geraniol 50?,-75?,, Nerol 257,-45?,, by weight.

A process for extracting Geraniol Coeur by steam distillation of grass of the plant Cymbopogon Martini is disclosed in U.S. Patent No. 5,753,686.

Until the invention, the use of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG as an insect repellent for people has had limited use in frangrances, which did not include use as a repellent. Never in the prior art has a vapor of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG emitted from a carrier not applied to the skin been used as the repellent. Applicant has discovered that only a very small amount of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor is necessary to repel insects including, without limitation, mosquitoes flies, gnats, and fleas.

The invention is also based, in part, on the discovery of a volatile material that is compatible with Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG. The volatile material is mixed with Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG to form an insect repellent solution. It has been found that a fragrance oil that has a large amount of residual ingredients at short term exposures to 170°F-195°F is a volatile material which can carry molecules of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor into the atmosphere where they are dispersed and act as a repellent against insects. Advantageously, the liquid system formed from the solution of fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG can be molded into solid plastic pellets which can then be molded into utilitarian objects, e.g., wrist bands and ankle bands, capable of repelling insects can be fabricated by conventional methods. Insect repelling wrist and ankle bands can contain between 207, and 307, Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and approximately 57, fragrance, by weight.

The liquid system formed from the solution of fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG can be mixed into a wax from which candles are molded. Also, the liquid system formed from the solution of fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG can be or placed in a solution of alcohol or water/alcohol in conjunction with a wick system to disperse the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor into the atmosphere in order to repel insects from a specific locale. The same solution can be applied to towelettes, i.e., small disposable towels, which can then be used as applicators to apply the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG based repellent solution to areas of the body of a person, for example, the wrists and elbows, from which the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG can be dispersed into the local atmosphere to repel insects from the region surrounding person.

In one embodiment of the invention an insect repellant system is created by a mixing a liquid system containing volatile fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and imbedding the liquid system within a thermoplastic resin system. In order to prevent flashing off of the volatile fragrance oil during the molding process, a thermoplastic system that can be molded at temperatures at approximately 200°F (93°C) must be used. There are fragrance systems that can be designed to be used for molding above 200°F, but they are not as effective in repelling insects.

The Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance oil can be used in liquid form or incorporated into a thermoplastic system such as polyethylene or polystyrene in conjunction with copolymers to form a solid product which can be molded at elevated temperatures to form utilitarian products having insect repellent qualities. The liquid formulation containing Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, both natural and synthetic, repels many insects and anthropods that carry and transmit diseases to human beings, and animals such as dogs and cattle. This general, safe, and non-toxic repellent has been found to repel fire ants, ticks, aedes aegypti mosquitoes, mosquitoes of the anopheles family, blackflies, and fleas. Many fragrance oils are incapable of withstanding the temperatures of a molding process, even at the aforementioned relatively low molding temperatures. It is therefore important to select a fragrance oil which does not have substantial amounts of low volatile ingredients, i.e., top notes, that would flash off during the molding process. The fragrance oil into in which the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG is mixed to form the liquid system employed in the invention must contain ingredients that can retain the intended odor or fragrance, after subjection to molding temperatures ranging between 180°F and 200°F ( 82.2°C-93.3°C) for periods of up to approximately 15 seconds.

It is been found that the polymeric thermoplastic system into which the solution of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance oil is incorporated during molding can include polyethylene in an amount ranging from 807, to 90?> by weight and ethylene vinyl acetate (EVA) copolymer in an amount ranging from 107, to 207, by weight, with a combination melt index of 24. In the preferred embodiment of the invention, the thermoplastic system includes 907, polyethylene and 10° ethylene vinyl acetate (EVA) co-polymer by weight. Alternatively, the polymeric thermoplastic system into which the solution of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance oil is incorporated during molding can include polyethylene in an amount ranging from 707, to 907, by weight and ethylene n-butyl acrylate copolymer in an amount ranging from 107, to 30'., by weight. In the preferred embodiment of the invention, the thermoplastic system includes polyethylene in an amount 807, by weight and ethylene-n butyl acrylate copolymer in an amount 207, by weight.

A fragrance oil suitable for mixing with Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and having the characteristics of sufficiently low volatility to prevent excessive flash off during molding with capability to disperse Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG in solution with the fragrance oil as a vapor into the atmosphere may be formulated from the following components.

Ingredient Percent

Heliotropine 5.67,

Cyclamen Aldehyde 5.157, Hydroxycitronellal 3.037,

Phenyl Ethyl Alcohol 2.247,

Linalool 8.967, Linalyl Acetate 2.247,

Geraniol 1.247,

Propylene Glycol 1.247,

Aldehyde C-ll (Undecylenic) 0.347, Aldshyde C-12 (Laurie) 0.567,

Citronellol 7.847,

Phenyl Ethyl Acetate 0.457,

/Amyl Cinnamic Aldehyde 12.32?

Benzyl Acetate 7.207' Terpineol Alpha 10.08?,

Terpinyl Acetate 10.087,

Eugenol U.S. P. 7.17?,

Ethyl Vanillin @ 10.0?, PG 2.247,

Aldehyde C-12 (Laurie) @ 10.07, PG 0.567, Geranium Chinese 3.367,

Benzoin Siam Resin IS @ 50.07, BB 1.127,

Lilial 4.00? n-amyl Salycylate 3.00?,

Total 100.00.

The foregoing ingredients are used in the preferred embodiment of the invention. Variations may be made within the scope of the invention.

To form a solid Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor emitting insect repellent m accordance with the invention, Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG is added to the above described liquid fragrance oil in concentrations dependent upon the final concentration of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG desired in the final polymeric product. The concentration of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG in the liquid system can be varied between 1% and approximately 20?, by weight. Example 1 Over 85% of Aedes aegypti mosquitoes in a 12 cubic foot cage were repelled by the insect repelling wristband for up to 60 hours. At 30% liquid load (25% Geraniol, 5?, fragrance), the Timed Vapor Release System allowed for a loss of 17?, of the liquid over a 72 hour period. Not only did the Geraniol Coeur allow for a greater liquid loading than DEET in the polyethylene matrix, but it also allowed for a greater release of the active ingredient in a shorter period of time.

An example of a liquid formula that repels most flying insects and dangerous or disease carrying anthropods such as ticks is the following:

Geraniol Coeur 30 lbs

Mineral Oil 38 lbs

Aloe Vera 1 lbs

Fragrance 3 lbs Isopropyl Myustate 10 lbs

Octyl Isononoate 3 lbs

Isopropyl Palmitate 15 lbs

Total 100 lbs

This formulation allows for a timed vapor release of the active ingredient (in this case Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG into the atmosphere, which results in the repelling of insects and anthropods before they land. For example, mosquitoes would not land on the surface of the skin before they are repelled by the active ingredient.

The repellent of the invention repels ticks, and red fire ants, and can be placed on the skin under the individual's clothing. DEET (N, N-diethyl-m-toluamide) is a toxic product used for repelling insects. It is not as effective in repelling insects or ticks as Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG . The timed vapor release formulation of the invention allows the active ingredient, Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, to vaporize through an individual's clothing, saturating it with the vapor resulting m the repelling of ticks without the use of highly toxic sprays on the clothing. The formulation of the invention can repel the aforementioned insects and ticks for a minimum of four hours.

A DEET wrist band according U.S. Patent No. 5,738,862, although admirably effective, does not repel as well as the Geraniol Coeur band of the present invention when exposed to Aedes aegypti mosquitoes. Moreover, tests have proved that the Geraniol based formulations of the invention outperform commerically available DEET products in repelling various insects and anthropods.

The fragrance oil, which can include mineral oil, acts as both a moisturizer for the skin and a matrix that allows for the slow release of both the fragrance and Geraniol Coeur vapor. The use of high-end ingredients for the fragrance allows for an extended release time of the Geraniol Coeur vapor to a point where the repellency is effective for up to 8 to 10 hours. Example 2

A formulation, in a polymer matrix, of Geraniol Coeur and a fragrance carrier in accordance with the invention was prepared. The weight of the formulation was measured over a 72 hour period to determine the rate of evaporation into the air to repel ticks.

Table 1 shows the weight loss of the formulation due to evaporation for three samples weighing 5.18 grams, 5.33 grams, and 5.24 grams, respectively, over the 72 hour period. The data of Table 1 is plotted in Fig. 1. The effectiveness of a wrist band containing my Geraniol Coeur and fragrance formulation is expected to last well over 100 hours. Example 3

Biting intensity of the American dog tick (Ambloyomma variegatum) (Dermacenter variabilis (Say) ) was compared for various tick repellents. The formulations tested included Blood Agar Attractant, Skin Sosoft, Off-Skinstastic, Repello Deet Based Towelette (187, DEET) and Repello Naturale Ticksafe. The Repello Naturale Ticksafe containing the formulation of the invention, i.e., a mixture of Geraniol Coeur and a volatile fragrance oil resulted in significantly fewer tick bites than the other products. The results of the test are shown in Fig. 2. Example 4

A Laboratory Olfactometer was adapted to measure tick response to artificial skin treated with selected semiochemicals . Ten treated skin surfaces were evaluated. The most active hosts selected for comparison were membrane covered blood packets with blood and glycerin treated air flowing over the surface, Various other materials were also tested to determine if more suitable hosts could be selected for future trials. The air treatment with blood and glycerin (3943 Glycerin (A)) was used as an attractant host to compare the effect of 3944 Geraniol Coeur (S) skin treatment to measure repellent action. Tests of the multi-choice open type were run for 8 hours. The tick (Amblyomma ameri canυm) feeding response was then measured in average bite seconds/hour. See Fig. 3A.

Five replications were made with treatments randomized within each replication. Overall treatment effectiveness was determined by analysis of variance among comparisons of the sums^' of activity for 8 hours demonstrating significant differences (p>.05) for the test. Comparison of exposure for 3943 blood and glycerin treated air and 3943 treated with 3944 Geraniol Coeur (S) was made using the one tailed t test. These comparisons were used to determine significant differences between the treatment with 3944 Geraniol Coeur (S) and the base treatment 3943. The significant difference demonstrated repellent activity for Geraniol Coeur when applied to the skin. Example 5

A Laboratory Olfactometer was adapted to measure tick response to artificial skin treated with selected semiochemicals. Ten treated skin surfaces were evaluated. The artificial host selected for comparison was membrane covered blood agar and feeding stimulants with blood and glycerin treated air flowing over the surface. See Table 3. The air treatment with blood and glycerin (A943 Glycerin STD Air TRT) was used as an attractant host to compare the effect of attractants and repellents against the activity of S929

Geraniol Coeur Skin treatment to measure its repellent action.

Tests were multi-choice open tests run for 8 hours. The tick

(Amblyamma americanum ) feeding response was then measured in mean bite seconds/hour. Eight replications were made with treatments randomized within each replication. Overall effectiveness was determined by analysis of variance among comparisons of the sum of activity for 8 hours significant differences (p>.05) for the test. Comparison of exposure for the standard host A943 (Glycerin STD Air TRT) and treatment with either S929 Geraniol Coeur Skin (.002g) and S906 Off SkintasticC) (.002g) were made using the one tailed t test. Both treatments demonstrated highly significant repellent activity with no significant differences between their activity. Further comparisons were made for activity of the two repellents placed in the airstream. Treatment A906 Off SkintasticO (.005g) and A929 Geraniol Coeur Air (.005g) treatment had higher but not significantly different tick activity than the standard A943 Glycerin STD AIR TRT. See Figs. 3.

Fire ants are another example of an insect that can be repelled by the above liquid formulation when applied to the skin as well as on clothing for example under an individual's socks. One can also spray the socks with the same material to repel fire ants from attacking the ankle and calf area. The repellent of the present invention can also be used to repel horn flies from cattle It will also repel mosquitoes and house flies. All of these insects cause stress and possible disease m cattle.

Losses m the production of milk and beef can be minimized by using approximately 1/2 to 1?> of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG with a solubilizmg agent such as polysorbate 20. Approximately 10 - 40 milliliters of an alcohol such as ethanol or isopropanol m which the repellent is suspended can be applied to a cow from its head to its back line. This amount will repel mosquitoes, house flies, and horn flies for up to five days at a minimum. Other formulations can extend that time.

Insect and tick repellent wrist bracelets can be fabricated m accordance with the invention. A thermoplastic system including polyethylene or polystyrene m conjunction with copolymers melts in the range of 150 degrees F to 225 degrees F. In accordance with the invention, a thermoplastic system containing a fragrance oil carrier and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG as an active ingredient for repelling insects, in conjunction with a specifically formulated fragrance oil as described herein, is molded in a closed, i.e., air-tight, system to minimize escape of the volatile constituents. Molding is done at a nominal temperature range of 180 degrees F to 200 degrees F in the closed system. By overloading the thermoplastic system in its liquid form with Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG in the closed system up to 20 percent of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance can be retained in the molded product.

The intertwining of polymeric domains results in an association complex with Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance ingredients in a liquid state contained within the thermoplastic system. The Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG rises to the surface of the thermoplastic material and, with the fragrance components retained after molding, is vaporized thereby enabling it to repel insects without requiring contact of the insects with a surface on which the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG is deposited.

Candles which can be burned to release Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor into the atmosphere to repel insects. Moreover, the liquid system formed from the solution of fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG can be or placed in a solution of alcohol or water and alcohol and dispersed through capillary action in a wick system and evaporation of the fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor into the atmosphere. In the alternative, the vapor can be mechanically dispersed into the atmosphere by a fan.

Another application for the mixture of a low-volatile material such as Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance is in the manufacture of insect repellent candles. The combination of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance can be placed in a wax melt which is poured or pressed into a candle mold and then solidified. The resulting candle will repel insects when it is burned. The heat radiated by the burning of the candle warms the wax distant enough from the flame to avoid decomposition but near enough to experience increased molecular motion to release a vapor of the fragrance which carries the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and creates a repelling environment for insects. The repellent action of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG carried by the fragrance vapor released from the candles is many times more effective than DEET or citronella candles. The pressed candle repels insects, due to the action of the timed vapor release system, without being lit. Unlike Citronella candles, the Geraniol-fragrance candles are smoke free.

The ineffectiveness of citronella candles has been reported in the Journal of the American Mosquito Control Association, Vol. 12, No. 2, pp. 293-94 (1996), in an article entitled "Evaluation of the Efficacy of 3% Citronella Candles and 5% Citronella Incense for Protection Against Field Populations of Aedes mosquitoes", Lindsay et al . The authors reported a study of the efficacy of commercially available citronella candles. Experiments were performed on live subjects. The authors concluded that "citronella candles... were ineffective for reducing the biting pressure of mosquitoes, and their use by the general public should be discouraged."

In the formation of a liquid airwick repellent system, either ethyl alcohol or a combination of ethyl alcohol and water can be added to the fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG solution. The addition of water added to the system has the effect of retarding the rate of evaporation of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor. For highest rates of evaporation, the liquid fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG solution is mixed with ethyl or isopropyl alcohol and no water. The following percentages of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, fragrance oil, water and alcohol are preferred: Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG 10?,, fragrance oil 5?,; alcohol 59?,; water 8',; and isopropyl pal itate, a surfactant, 187,. The surfactant is required to enable the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG to mix with the water and alcohol base of the liquid which is vaporized in the airwick. The alcohol in the foregoing mixture may be varied in the range of 107, to 80% by weight whereas the amount of water can be between 5% and 307, by weight. Water is added to the solution to decrease the evaporation rate of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor repellent while extending the life of the system. There is a limitation on the proportion of water that can be added in that only an amount of water which will allow for complete dissolving of all of the organic ingredients can be added. Since the organic ingredients, i.e., fragrance oil and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG, are not soluble in water unless surfactants are used. The limiting factor is the solubility of the solution of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and the fragrance in the water and ethyl or propyl alcohol solution.

Unlike Citronella applicators, the towelette of the instant invention has a vapor release mechanism. In using prior art towlettes, one must apply the repellent to all exposed parts of the body, i.e., arms, neck, face, and legs. These prior art products depend on an insect approaching and coming in contact with the exposed area of an individual. Therefore, the individual must use the prior art product so as to cover all of the exposed skin.

With the towelette of the invention, one only need apply the towelette around the wrists and elbows if the concentration of ticks and insects s relatively low. The formulation allows the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor to escape to areas surrounding the body resulting in the repelling of ticks on adjacent clothing and insects, including flying insects which have not yet landed. The percentage of the area of required coverage of the body depends upon the concentration of ticks and insects. In typical situations, one towlette can contain a sufficent amount of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG repellent solution to be used to protect many people. The ability of several persons to share a single towelette enhances economy associated with the protection of groups of people.

The fragrance oil, which can include mineral oil, acts as both a moisturizer for the skin and a matrix that allows for the slow release of both the fragrance and Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor.

The use of high-end ingredients for the fragrance allows for an extended release time of the Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor to a point where the repellency is effective for up to 8 to 10 hours.

Experiments carried out with wax and a combination of Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG and fragrance show that both Geraniol, Geraniol Coeur, Geraniol CFT, and/or Geraniol RG vapor and the fragrance are released into the environment on the burning of the candle. A candle formulated with the fragrance described m my U.S. Patent No. 5,738,862 at a concentration of 2',, and Geraniol at a concentration of 4% by weight, mixed with paraffin wax covers approximately 100% more area than a repellent than without the fragrance. Test results show that the Geraniol candle is 100% more effective than a Citronella candle in repelling flying insects .

Example 6

The testing of the candle in a cage was conducted in a twelve cubic foot chamber with airing ports. The cage contained approximately 150 aedes aegypti mosquitoes. The candles were allowed to burn for twenty minutes and the number of mosquitoes repelled was recorded for the next sixty minutes. The mosquitoes that were repelled escaped to a second cage. Over 957, of the mosquitoes escaped to the outside cage. For the control, counts were made in a similar manner, but no candle was burned. Only approximately 157, of the mosquitoes left the test cage.

Example 7

Bait for red fire ants was prepared from .6 gms . corn starch, .4 gms. ground course peanuts, .05 grams calcium silicate, and 0.2 gms. of various test materials. The bait without any test material, and with each of 7 different test materials was exposed to ants. The number of ants coming in contact with the bait was measured. The results are plotted in Fig. 4. Example 8

Artificial hosts, Skin (S) , were exposed to a population of Rocky Mountain Wood Ticks (dermacenter variabilis) . The number of seconds during which contact of the ticks with the host occured was measured for the host without repellent, and with each of five repellents. The resultant data are tabulated in Table 5 and the averages are plotted in Fig. 5. The host protected with the Geraniol formulations (The Repello Naturale Ticksafe) containing the formulation of the invention, i.e., a mixture of Geraniol Coeur and a volatile fragrance oil resulted in significantly fewer tick bites than the other products. There was minimal contact in comparison with the host alone, and the host protected by the other repellents. Example 9 The foregoing test was repeated with blood and glycerin treated air flowing over the surface of the hosts. The resultant data are tabulated in Table 6 and the averages are plotted in Fig. 6. The host protected with 3962A Repello Geraniol Coeur had minimal contact in comparison with the host alone, and the host protected by the other repellents. Example 10

Skin (S) was exposed to a population of Lone Star Ticks

(Amblyomma ameri canum) . The number of seconds during which contact of the ticks with the host occurred was measured for the host without repellent, and with each of three repellents.

The resultant data are tabulated in Table 7 and the averages are plotted in Fig. 7. The host protected with S929 Geraniol Coeur Skin, i.e., a mixture of Geraniol Coeur and a volatile fragrance oil had minimal contact in comparison with the host alone, and the host protected by the other repellents. Example 11 The foregoing test was repeated with blood and glycerin treated air flowing over the surface of the hosts. The resultant data are tabulated in Table 8 and the averages are plotted in Fig. 8. The host protected with 3944 Geraniol Coeur, i.e., a mixture of Geraniol Coeur and a volatile fragrance oil, had the least contact in comparison with the host alone, and the host protected by the other repellents. Example 12

Bite second responses from 8-hour exposures to a population of Lone-Star Ticks were made. The data are shown in Fig. 9 and Table 9. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts.

Example 13

Contact responses from 8-hour exposures to a population of American Dog Ticks were made. The data are shown in Fig.

10A-B and Table 10A-B. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts.

Example 14 Bite second responses from 8-hour exposures to a population of Culex pipiens quinquefaciatus were made. The data are shown in Fig. 11 and Table 11. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Example 15

Bite second responses from 8-hour exposures to a population of aedes aegypti mosquitoes were made. The data are shown in Fig. 12. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Example 16 Bite second responses from 8-hour exposures to a population of aedes aegypti (Linnaeus) yellow fever mosquitoes were made. The data are shown in Fig. 13 and Table 12. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Example 17

In order to test the effectiveness of the invention with respect to equine applications, a 20?, concentration of Geraniol in a solution containing 78 mineral oil, 1.', Aloe Vera and 1% fragrance, was applied to 2 horses in the following manner: The individuals applying the solution gloved themselves and used a shimmy like applicator on each horse. Approximately 50 milliliters of the solution was applied to each horse. A whole wipe down of each horse was performed. House flies (Musca domestica Linnaeus), stable flies (Sto oxys calcityrans (Linnaeus) ) , horn flies Horn Fly (Haematobia irritans (Linnaeus)), and culicoides (No See-Urns gnats) were repelled for over 4 hours. Laboratory evaluations utilizing an electronic olfactometer confirmed the repellent action of a 20% Geraniol solution against house flies, stable flies and horn flies. The data are presented in Figs. 14 A-D. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Example 18

In order to test the effectiveness of the invention with respect to livestock, cattle in a horn fly and house fly environment were treated with 30-50 milliliters a Geraniol solution which was applied down the top lines of their bodies. The solution was made up of 307, Geraniol, 17, Aloe Vera, 1% fragrance and 687, mineral oil. In all cases the Geraniol solution repelled the horn flies and house flies. Laboratory evaluations utilizing an electronic olfactometer confirmed the repellent action of this Geraniol solution against house flies, stable flies and horn flies. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Example 19 Bite second responses from 8-hour exposures to a population of Anopheles quadrimaculatus Say, malaria spreading mosquitoes were made. The data are shown in Figs. 15 A-C. The mixture of Geraniol Coeur and a volatile fragrance oil described above gave favorable results, i.e., fewer contacts. Similar tests show the mixture of Geraniol Coeur and a volatile fragrance oil to repel cat fleas (Ctenocephalides felis) . Referring now to Fig. 16, a solution 1 of Geraniol and fragrance can also be placed in a container 2 covered by a centrifugal fan 4. In the preferred embodiment of invention, the fan 4 has 18 blades. The fan 4 can be driven by a motor 6 which, in the preferred embodiment of invention, operates at 673 r.p.m. which has been found to be idea for a 12' x 15' x 8' space. The motor is connected to a source of voltage, e.g., a D cell battery 8. The fan and container are desirably placed in a housing having 230 degree circular intake/outflow vents for evenly dispersing the mixture into the surrounding air.

When the fan 4 is turned on, the vapors from the solution are drawn into the fan and the molecules of Geraniol and fragrance are then dispersed into the air. The solution can contain between 20% and 307, Geraniol and 707, - 80% mineral oil and 1% - 3% fragrance. Alternatively, the solution can contain 207, to 307, Geraniol, 507, mineral oil, mixed with any combination of ethyl and isopropyl alcohol, with or without, 17, - 3% fragrance. The dispersion of the Geraniol spray in a barn is effective in preventing flying insects from attaching themselves to cattle and other animals, and in preventing insects from landing on animals. The spray can be released at predetermined times by connecting a timer 10 between the fan and its power supply. Release of the spray into the air repels of insects such as mosquitoes, house flies, stable flies and other insects known to inhabit an area in and around barns. In barns, a preferable formulation contains 20% - 907, Geraniol and 3% fragrance, with the remainder consisting of ethyl and/or isopropyl alcohol.

It is also known that maggots affect the rectal areas of sheep throughout the world. The use of Geraniol in conjunction with a toxicant such as permethrin (0.5%) is able to control maggot infestation of sheep and also repel annoying insects that affect the breeding and health of sheep. An effective formulation suitable for application to the rectal area of a sheep is as follows: 207-307, Geraniol, 68' -78', mineral oil, 1.5% Aloe Vera and .5% permethrin. Permethrin acts as a toxicant that kills maggots. The Geraniol portion of the formulation repels annoying insects.

It is to be appreciated that the foregoing is a de- scription of a preferred embodiments of the invention to which variations and modifications may be made without departing from the spirit and scope of the invention.

Claims

What is claimed is:

1. A repellent for ticks, red fire ants, and insects comprising a liquid system consisting of Geraniol and a fragrance oil.

2. A repellent for ticks, red fire ants, and insects in accordance with claim 1 wherein the Geraniol is present in an amount in the range of 5% to 30% by weight of the liquid system.

3. A repellent for ticks, red fire ants, and insects in accordance with claim 1 wherein the fragrance oil has residual ingredients that are retentive above 170┬░F.

4. A repellent for insects in accordance with claim 1 further comprising a thermoplastic system.

5. A repellent for insects in accordance with claim 4 wherein the thermoplastic system comprises polyethylene.

6. A repellent for insects in accordance with claim 5 wherein the thermoplastic system comprises polyethylene in an amount ranging from 70% to 90% by weight and ethylene vinyl acetate (EVA) co-polymer in an amount ranging from 107, to 207, by weight.

7. A repellent for insects in accordance with claim 5 wherein the thermoplastic system comprises polyethylene in an amount ranging from 707, to 90% by weight and ethylene-n butyl acrylate copolymer in an amount ranging from 10' to 30', by weight.

8. A repellent for insects in accordance with claim 4 wherein the thermoplastic system comprises polystyrene.

9. A repellent for insects in accordance with claim 4 wherein the thermoplastic system comprises polyvinyl acetate.

10. A repellent for ticks, red fire ants, and insects in accordance with claim 1 further comprising ethyl alcohol in an amount in the range of 10% to 80% by weight.

11. A repellent for ticks, red fire ants, and insects in accordance with claim 10 further comprising water in an amount in the range of 5% to 30% by weight.

12. A repellent for ticks, red fire ants, and insects in accordance with claim 8 further comprising an air-wick means for absorbing said mixture of alcohol, fragrance oil and Geraniol and dispersing it into the atmosphere.

13. A repellent for insects in accordance with claim 1 further comprising wax.

14. A repellent for insects in accordance with claim 13 wherein the wax is molded into a candle.

15. A method of making a composition for repelling ticks and insects comprising mixing a low volatility repellent for ticks, red fire ants, and insects having a boiling point greater than 320┬░F with a mixture of low and middle note fragrance ingredients having a boiling point of less than 170┬░F to lower the vaporization point of the repellent for ticks and insects thereby increasing the volatility of the repellent for ticks and insects whereby it vaporizes at ambient temperatures at sufficient rates to repel ticks and insects.

16. A repellent candle for insects, said candle comprising a mixture of Geraniol, a fragrance oil, and wax.

17. A repellent applicator for topical application to the skin of a person for repelling ticks, red fire ants, and insects, said applicator comprising an absorbent towelette containing a mixture of an alcohol, a fragrance oil and Geraniol, said towelette being adapted to be applied to an area of a body for transferring a quantity of said mixture thereto whereby the mixture releases Geraniol vapor into the atmosphere to repel ticks and insects from the region surrounding the body.

18. A method of repelling ticks, fire ants and insects from around the body of a person comprising moistening a towelette in a mixture of an alcohol, a fragrance oil and Geraniol, and touching the towelette to an area of a body for transferring a quantity of said mixture thereto whereby the mixture releases Geraniol vapor into the atmosphere to repel ticks and insects from the region surrounding the body.

19. A molded plastic for use in the manufacture of an article that can repel flying insects before the insects can land on a surface of the article comprising a thermoplastic material which is has a melting point of not greater than 225 degrees F, and a liquid repellent for flying insects imbedded in the thermoplastic material during molding thereof, the liquid repellent for ticks and insects including a mixture of

Geraniol and a fragrance oil having volatile fragrance components and retentive components which prevent flash off of the fragrance components, the flash off temperature of the fragrance oil being greater than the melting point of the thermoplastic material, the imbedded liquid repellent for flying insects rising to the surface of the molded plastic at ambient temperatures so that portions of the fragrance components are vaporized and carry with them portions of the Geraniol into the proximate atmosphere to repel flying insects before they can land.

20. A molded plastic in accordance with claim 19 wherein the melting point of the thermoplastic material is no greater than 200┬░F.

21. A molded plastic in accordance with claim 19 wherein the flash off temperature of the fragrance oil is no less than 200┬░F.

22. A molded plastic in accordance with claim 19 wherein the thermoplastic material consists of polyethylene and at least one ethylene copolymer.

23. A molded plastic in accordance with claim 22 wherein the copolymer consists of polyethylene vinyl acetate.

24. A molded plastic in accordance with claim 23 wherein the polyethylene is present in an amount in the range of 807 to 90% by weight of the thermoplastic material and the polyethylene vinyl acetate is present in an amount in the range of 10% to 20% by weight of the thermoplastic material.

25. A molded plastic in accordance with claim 22 wherein the copolymer consists of polyethylene-n butyl acrylate.

26. A molded plastic in accordance with claim 25 wherein the polyethylene is present in an amount in the range of 70^to 90% by weight of the thermoplastic material and the polyethylene-n butyl acrylate is present in an amount in the range of 10% to 30% by weight of the thermoplastic material.

27. A molded plastic in accordance with claim 26 wherein the polyethylene is present in an amount of 80% by weight of the thermoplastic material and the ethylene-n butyl acrylate is present in an amount in the range of 20% by weight of the thermoplastic material.

28. A molded plastic in accordance with claim 19 wherein the Geraniol is present in an amount of 1% to 30% by weight of the liquid repellent for ticks and insects.

29. A molded plastic in accordance with claim 19 wherein the thermoplastic material comprises polystyrene.

30. A method of making a molded plastic for use in the manufacture of an article that can repel flying insects before the insects can land on a surface of the article comprising preparing a liquid repellent for insects by mixing Geraniol with a fragrance oil having volatile fragrance components and retentive components which prevent flash off of the fragrance components, molding a mixture of a thermoplastic material having a melting point of not greater than 225 degrees F and said liquid repellent for ticks and insects at a temperature greater than the melting point of the thermoplastic material and less than the flash off temperature of the fragrance oil in an air-tight environment to embed the liquid repellent for ticks and insects within the thermoplastic material, such that the imbedded liquid rises to the surface of the molded plastic when solidified at ambient temperatures so that portions of the fragrance components are vaporized and carry with them portions of the Geraniol into the proximate atmosphere to repel flying insects before they can land.

31. A method of making a molded plastic in accordance with claim 30 wherein the mixture is molded at a temperature in the range of 180┬░F - 200┬░F.

32. A method in accordance with claim 31 wherein the thermoplastic material consists of polyethylene and at least one ethylene copolymer.

33. A method in accordance with claim 32 wherein the copolymer consists of polyethylene vinyl acetate.

34. A method in accordance with claim 33 wherein the polyethylene is present in an amount in the range of 707, to 907, by weight of the thermoplastic material and the polyethylene vinyl acetate is present in an amount in the range of 107, to 20% by weight of the thermoplastic material.

35. A method in accordance with claim 32 wherein the copolymer consists of polyethylene-n butyl acrylate.

36. A method in accordance with claim 35 wherein the polyethylene is present in an amount in the range of 70 to 907, by weight of the thermoplastic material and the polyethylene-n butyl acrylate is present in an amount in the range of 107, to 30% by weight of the thermoplastic material.

37. A method in accordance with claim 36 wherein the polyethylene is present in an amount of 80% by weight of the thermoplastic material and the polyethylene-n butyl acrylate is present in an amount of 20% by weight of the thermoplastic material.

38. A method in accordance with claim 30 wherein the thermoplastic material comprises polystyrene.

39. A candle for repelling flying insects comprising a body of wax material which has a melting point of not greater than 225 degrees F, and a liquid repellent for flying insects imbedded in the wax material during molding of the candle, the liquid repellent for ticks and insects including a mixture of Geraniol and a fragrance oil having volatile fragrance components and retentive components which prevent flash off of the fragrance components, the flash off temperature of the fragrance oil being greater than the melting point of the wax material, whereat when the candle is lit, portions of the fragrance components are vaporized and carry with them portions of the Geraniol into the proximate atmosphere to repel flying insects .

40. A candle in accordance with claim 39 wherein the melting point of the wax material is no greater than 200┬░F.

41. A candle in accordance with claim 39 wherein the flash off temperature of the fragrance oil is no greater than

200┬░F.

42. A candle in accordance with claim 39 wherein the Geraniol is present in an amount of 1% to 30% by weight of the liquid repellent for ticks and insects.

43. A method of making a candle for use in repelling flying insects before the insects can land on a surface in proximity to the candle comprising preparing a liquid repellent for ticks and insects by mixing Geraniol with a fragrance oil having volatile fragrance components and retentive components which prevent flash off of the fragrance components, molding a mixture of candle wax and said liquid repellent for ticks and insects at a temperature greater than the melting point of the candle wax and less than the flash off temperature of the fragrance components to embed the liquid repellent for ticks and insects within the candle wax, whereat when the candle is lit, portions of the fragrance components are vaporized and carry with them portions of the Geraniol into the proximate atmosphere to repel flying insects before they can land.

44. A method of making a candle in accordance with claim 43 wherein the candle is molded at a temperature of less than 200┬░F.

45. A method of repelling ticks, fire ants and insects from an environment comprising placing a mixture of an alcohol and Geraniol in a container, mounting a fan proximate said container, and activating the fan for drawing the mixture into said fan whereby molecules of the Geraniol are dispersed into the air within said environment for repelling said ticks and insects .

46. A method according to claim 45 wherein said mixture consists of between 20% and 30% Geraniol and 70% - 80% mineral oil, by weight.

47. A method according to claim 45 wherein said mixture consists of between 20% to 30% Geraniol, 50% mineral oil, and any combination of ethyl and isopropyl alcohol, by weight.

48. A method of repelling ticks and insects from a barn comprising placing a liquid mixture of an alcohol and Geraniol in a container within said barn, and spraying the mixture into the air within said barn at predetermined times for repelling said ticks and insects from cattle and other livestock in the barn.

49. A method according to claim 48 wherein said mixture consists of 20% - 90% Geraniol, 37, fragrance, and, 77, - 77% ethyl and/or isopropyl alcohol by weight.

50. A method of repelling ticks, insects and maggots from sheep comprising applying to the rectal area of the sheep a mixture consisting of 207,-30% Geraniol, 687,-78? mineral oil, 1.5% Aloe Vera and 0.5% permethrin.

51. A method of repelling ticks and insects from horses comprising applying to them a solution consisting of 20% Geraniol, 78% mineral oil, 1% Aloe Vera and 1% fragrance, by weight.

52. A method of repelling ticks and insects from cattle comprising applying to them a solution consisting of 30% Geraniol, 1% Aloe Vera, 1% fragrance and 68% mineral oil.