CA1281999C - Composition and method for repelling insects - Google Patents
Composition and method for repelling insectsInfo
- Publication number
- CA1281999C CA1281999C CA000544473A CA544473A CA1281999C CA 1281999 C CA1281999 C CA 1281999C CA 000544473 A CA000544473 A CA 000544473A CA 544473 A CA544473 A CA 544473A CA 1281999 C CA1281999 C CA 1281999C
- Authority
- CA
- Canada
- Prior art keywords
- mole percent
- alkene
- carbon atoms
- polymer
- maleic anhydride
- 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.)
- Expired - Fee Related
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/10—Insect repellent
Abstract
ABSTRACT
This invention relates to volatile insect repellent compositions comprising an insect repellent, such as deet, and specific maleic anhydride/alpha olefin polymers to increase the residual activity of the insect repellent.
This invention relates to volatile insect repellent compositions comprising an insect repellent, such as deet, and specific maleic anhydride/alpha olefin polymers to increase the residual activity of the insect repellent.
Description
3q3~
This invention relates to new and useful compositions of matter suitable as volatile insect repellents.
Insect repellents have historically been sel-5 ected on the basis of their persistence on the skin.
Unfortunately, the usual topically applied insect repellents, such as diethyl toluamide, are fairly vol-atile, and therefore, have the disadvantage of giving protection only for relatively short periods of time due 10 to their rapid evaporation and/or absorption by the skin.
Both problems, absorption and evaporation, necessitate frequent applications which are bothersome and time-consuming.
Adding adjuvant materials to increase the per-15 sistence of insect repellents was reported as early as1928 for a formula consisting of oil of citronella, spirits of camphor, oil of tar, oil of pennyroyal and castor oil Mehr et al., Laboratory E~aluation of Con-trolled-Release Insect Repellent Formualtions, J.Am.
20 Mosq. Control Assoc., Vol. 1(2):143 (June, 1985). The Mehr et al. researchers tested the persistence of several controlled-release formulations of diethyl toluamide, or more specifically, N,N-diethyl-3-methylbenzamide.
Diethyl toluamide is commonly known as deet. These 25 formulations consisted of microcapsule and free-repellent formulations containing hydrophilic vinyl polymers, such as polyvinylpyrrolidone.
U.S. Patent No. 2,808,359 discloses that ab-sorption by the skin and evaporation are reduced by ~r mixing insect repellents with hydroxyalkyl esters of dicarboxylic acids, including bis(2 ethyl~3-hydroxy-hexyl) maleate. Other patents also disclose the use of various materials to extend the residual activity of 5 insect repellents or slow release pesticides. See, for example, U.S. Patent Nos. 2,88~,355, 4,435,383 and 4,489,056.
U.S. Patent No. 4,358,573 teaches that maleic anhydride/alpha olefin terpolymers are useful as 10 mold release agents, slip agents and additives to floor polishes. They are not ~aid to increase the residual activity of volatile insect repellents.
Accordingly, the object of the present invention is to provide an insect repellent composition for topical 15 and/or surface application with improved residual ac-tivity, i.e., the period of repel-lent activity after application.
The present invention provides a composition having enhanced residual insect repellent activity 20 comprising at least one volatile insect repellent; char-acterized by the composition including at least one polymer consisting of about 49-60 mole percent maleic anhydride and about 51-40 mole percent of at least one l-alkene having 4-30+ carbon atoms, wherein the weight 25 ratio of insect repellent to polymer is from about 10:1 to 50:1 The compositions of the present invention unexpectedly prolong residual activity by reducing skin absorption and evaporation of the insect repellent.
It has been found that the compositions of the invention unexpectedly produce better repellency, i.e., they prolong the protection Crom mosquitoes and flies as compared with those formulations not containing a polymer of the invention.
It has also been unexpectedly found that the addition of a maleic anhydride/alpha olefin polymer to the insect repellent, deet, not only improves residual ~ 3~
activity, but also the tactile characteristics o~ the deet formulation as applied to the skin.
The preferred embodiments of the invention will now be described in detail. The volatile insect re-5 pellents that may be utilized in accordance with theteachings of this invention are those considered ef-fective against the particular insect targeted, and preferably, those compatible with the skin for topical applications.
Examples of volatile insect repellents ef-fective against mos~uitoes and biting flies include:
N,N-diethyl toluamide (deet); ethyl hexanediol; 2-(octyl thio) ethanol; dimethyl phthalate; di-n-propyl-2,5-pyridine dicarboxylate; 1,5a,6,9,9a,9b-hexahydro-15 4a(4h)-dibenæofuran carboxaldehyde; citronellal (3,7-dimethyl-6-octenal); citronellol (3,7-dimethyl-6-octen-1-ol); geraniol (trans-3,7-dimethyl-2,6-octadien-1-ol); nerol (c -3,7-dimethyl-2,6-oct-adien-l-ol); linalool (3,7-dimethyl-1,6-octadien-3-01);
20 and mixtures thereo~.
The concentration of repellent utilized in ac-cordance with the teachings of this invention is not critical. The lower limit is defined by that amount required to form an effective dosage, and the upper 25 limit, by economic considerations. The amount of insect repellent employed will vary depending on several fac-tors, including, the type of insect repellent, the targeted insect or insects, and the other ingredients utilized, e.g., the maleic anhydride polymer.
The concentration of insect repellent can preferably be from about i% to 90~, based on the total weight of the insect repellent composition. The pre ferred ranges are from about 1 to 25 percent, base on the total weight of the insect repellent composition.
35 Unless otherwise indicated, all percen-tages of in-gredients are calculated as weight percentages based on the total weight of the insect repellent compo-sition.
Other insect repellents, especially those well known in the art and useful for such purposes, can also 5 be readily utilized.
Maleic anhydride/alpha olefin polymers may be utilized, in accordance with the teachings of this in-vention, to increase insect residual activity. These polymers include compositions having (a) about 49 to 10 60 mole percent maleic anhydride and (b) about 51 to 40 mole percent of at least one l-alkene having from 4-30+
carbon atoms. Preferred maleic anhydride polymers have (a) about 49-55 mole percent maleic anhydride and (b) about ~5-51 mole percent of at least one l-alkene having 15 from 6-16 carbon atoms, with 8-12 carbon atoms being more preferred. A more preferred polymer has about 50 mole percent maleic anhydride and about 50 mole percent 1-decene.
Additional polymers that may be utilized in ?0 accordance with the teachings of this invention include the maleic anhydride/alpha olefin terpolymers disclosed in U.S. Patent No. 4,358,573. These are formed from monomers comprising: (a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of a least one 25 l-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one l-alkene having from 18-30~ carbon atoms.
Additionally, preferred maleic anhydride/alpha olefin polymers include: (a) about 49 to 55 mole per-30 cent maleic anhydride, (b) about 20 to 30 mole percentof at least one l-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of at least one l-alkene having from 18-24 carbon atoms; and also (a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole 35 percent of at least one 1 alkene havin~ from 8 12 car-bon atoms, and (c) about 20-30 mole percent of a mixture ~ 3~3 of l-alkenes consisting of about ~5-55 mole percent l-eicosene, about 40-55 mole percent l-docosene, and about 5-10 mole percent l-tetracosene.
The maleic anhydride/alpha olefin polymers are 5 generally present in amounts sufficient to reduce the evaporation and skin absorption of the ;nsect repe]lent.
Accordingly, these materials may be present in amounts from about 0.1 to 25 percent, based on the total weight of the insect repellent cornposition, with preferred 10 amounts ranging from about 1 to 5 percent.
It has been discovered, however, that the concentration of polymer is dependent on the concen-tration of insect repellent. Accordingly, a weight ratio of insect repellent to polymer from about 10:1 15 to 50:1 is desirable to attain the objectives of this invention. A weight ratio of 15:1 to 25:1 is more pre-ferred. The particular ratio selected is of course, dependent on the repellent, its volatility and the poly-mer utilized. If the ratio of repellent to polymer is 20 less than about 10:1, the polymer may tightly bind the volatile repellent, thereby preventing its release and repellent effect. If the ratio is greater than about 50:1, the repellent will usually be released too rapidly and the composition will rapidly lose its residual ac-25 tivity.
The application of these compositions is fac-ilitated by solution of the active ingredients in sol-vents, such as the lower alkanols, ethanol and the like, kerosene and similar petroleum oils, ethers, ketones, 3~ aldehydes and the like.
Additionally, the compositions of the pres-ent invention may be applied in aerosol form, in which case, the above-identified compositions may additionally contain a propellent or a mixture of propellents. The 35 type of propellent is not critical and any of those conventionally utilized can be employed to produce an aerosol formula. Typical propellents include isobutane, , 6 -propane, n-butane, and the like, and mixtures thereof, which are utilized in conventional amounts.
In preparing the compositions of -this invention, the insect repellent is generally added directly to an 5 alcoholic polymer solution which can then be formulated ox packaged in any form commonly used for such repellents, i.e., aerosol, pump spray, roll-on or lotion. It is clear to those skilled in the art that the anhydride group of the polymer is converted to the half alkyl 10 ester under these conditions, i.e., the presence of alcohol at room temperature.
In each of the following formulations, MAN=
maleic anhydride. The number or numerical range pre-ceding MAN is the mole percent of maleic anhydride in 15 the polymer. The group Cx Cx, denotes the nu~er of carbon atoms comprising the l-alkene. The number or numerical range preceding this designation is the mole percent of the l-alkene in the polymer.
Typical preparations of this invention 20 include:
~ 3~3 General Formula Amount (percent b~ weight) Ingredients Preferred More Preferxed Insect repellant l-90 1-25 Polymer 0.1-25 0.1-1.5 5 Carrier/propellant 0-99 73.5-99 Repellent:
Formula l Polymer Ingredien-ts Amount ~ by wt.) Ratio Deet 5-50 10:1 to 10 49-60 MA /51-40 C C 0 5-5 50:1 Carrier/propellent 45-95 Repellent:
Formula 2 Polymer I!ngredients Amount (% b~ wt.) Ratio 15 Deet 10-20 15:1 to 49-60 ~ /51-40 C8-C120.1-2 25:1 Carrier/propellent78-90 Repellent:
Formula 3 Polymer ngredientsAmount (~O by wt.) Ratio 20 Deet 15 15:1 50 MAN/50 ClO
Carrier/propellent 84 Repellent:
Fon~a 4 Pol~
IngredientsPmount (~O by wt.) Ratio 25 Deet 5-50 lO:l to 49-55 ~ /20-30-,c8-cl2 o. 5_5 50:1 Carrier/propellent 3''3'~
Repellent Formula 5 Polymer Ingredients Amount (% by wt.) Ratio Deet 10-20 15:1 to 5 49-55 MAN/20-30 C8-C12 0.1-2 25:1 Carrier/propellent 78-90 ~pellent:
Formula 6 Polymer 10 Ingredients Amount (% by wt.) Ratio Deet 15 15:1 Carrier/propellent84 Repellent:
Formula 7 Polymer IngredientsAmount(% by wt.) Ratio -Deet 5-50 10:1 to 49-55 MA /20-30 C8~C12 0.5-5 50:1 Carrier/~ropellent45-95 ~pellent:
Formula 8 Polymer IngredientsAmount ~% by wt.) Ratio 25.Deet ~ 10-20 15;1 to 49-55 MAN/20-30 C8-C12 0.1-2 25:1 20-30 C20-c2~-*/ '78-90 39~
Repellent:
Fo rmul d 9 Po lymer lngre~ients Amount (~ _t.) Ratio Deet 15 15:1 25 C20 C24**/
Carrier/propellent 84 */ The C20-C24 l-alkenes comprise 45-55 mole percent C20, 40 50 mole percent C22 and 5-10 mole percent c24.
**/ The C20-C24 l-alkenes comprise 50.1 mole percent C20, 43.4 mole percent C22 and 6.5 mole percent Fepellent:
15 Formula 10 Polymer In~redients Amount (~ by wt.) Ratio Deet 10-20 15:1 49-55 MAN/20-30c8-l2 0.1-2 20 Carrier/propellent 78-90 In order to illustrate the improved results obtained from the present invention, repellency tests were conducted to show the improvements in residual activity provided by the volatile insect repellent com-25 positions of the present invention. These testsl whichillustrate the scope of the invention but do not limit it, were carried out in the following manner:
The compositions of this invention having the formulations set forth in Table 1 were prepared by mixing an alcohol solution of the polymer with deet and a pro-5 pellent consisting of 75~ isobutane and 25% butane, andpackaging this formulation in standard aerosol cans.
The formulations were tested for their residual repellent activity against mosquit~es and flies for lands and bites as follows: the test insects were 10 adults, reared on 10% sucrose solutions, consisting of (1) about 6,000 mixed sex stable flies, Stomox s cal-cltrans, three weeks from peak emergence, or (2) about 4,000 mixed sex mosquitoes, Aedes aegypti, seven days from peak emergence, that were separately placed in screened 15 wooden cages. A test subject's forearm was thoroughly cleaned, treated with khe repellent material at a rate of 1 gram or 2 ml per 645 square cm. from the wrisk to the elbow, and then exposed to the test insects at pre-determined time intervals, usually one minute every 30 20 minutes, with the first exposure at 30 minutes after application. The observations noted were for repel-lency (no landing insects), lands (insect lands, but does not bite), and bites (insect lands and bikes).
The test was terminated when inseck bites were received 25 during two consecutive exposures. The longer the period between application and the time of first land and/or first bite, the more effective the insect repellent, i.e., the greater its residual activity.
The results in Table 1 demonstrate that at 30 least about a 10:1 weight ratio of insect repellent to polymer significantly increases the residual activity of the repellent, as measured by the time for the first mosquito or fly bite to occur, when compared to a con-trol formulation not containing a polymer of this invention.
~X~ 39 When the weight ratio deet to polymer was lowered to about 7.5:1, i.e., 15% deet and ~% polymer as in Formula B, the residual activity was somewhat better than a control ~ormulation not containing a 5 polymer of this invention. When the ratio of repellent to polymer was lowered still further to about 5:1 as shown in Formula A, the residual activity was inferior to the residual activity of a control formula not con-taining a polymer. It is believed that with ratios 10 lower than about 10:1, the polymer tightly binds the deet, preventing it from volatilizing, and thereby inhibiting its effectiveness as an insect repellent.
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This invention relates to new and useful compositions of matter suitable as volatile insect repellents.
Insect repellents have historically been sel-5 ected on the basis of their persistence on the skin.
Unfortunately, the usual topically applied insect repellents, such as diethyl toluamide, are fairly vol-atile, and therefore, have the disadvantage of giving protection only for relatively short periods of time due 10 to their rapid evaporation and/or absorption by the skin.
Both problems, absorption and evaporation, necessitate frequent applications which are bothersome and time-consuming.
Adding adjuvant materials to increase the per-15 sistence of insect repellents was reported as early as1928 for a formula consisting of oil of citronella, spirits of camphor, oil of tar, oil of pennyroyal and castor oil Mehr et al., Laboratory E~aluation of Con-trolled-Release Insect Repellent Formualtions, J.Am.
20 Mosq. Control Assoc., Vol. 1(2):143 (June, 1985). The Mehr et al. researchers tested the persistence of several controlled-release formulations of diethyl toluamide, or more specifically, N,N-diethyl-3-methylbenzamide.
Diethyl toluamide is commonly known as deet. These 25 formulations consisted of microcapsule and free-repellent formulations containing hydrophilic vinyl polymers, such as polyvinylpyrrolidone.
U.S. Patent No. 2,808,359 discloses that ab-sorption by the skin and evaporation are reduced by ~r mixing insect repellents with hydroxyalkyl esters of dicarboxylic acids, including bis(2 ethyl~3-hydroxy-hexyl) maleate. Other patents also disclose the use of various materials to extend the residual activity of 5 insect repellents or slow release pesticides. See, for example, U.S. Patent Nos. 2,88~,355, 4,435,383 and 4,489,056.
U.S. Patent No. 4,358,573 teaches that maleic anhydride/alpha olefin terpolymers are useful as 10 mold release agents, slip agents and additives to floor polishes. They are not ~aid to increase the residual activity of volatile insect repellents.
Accordingly, the object of the present invention is to provide an insect repellent composition for topical 15 and/or surface application with improved residual ac-tivity, i.e., the period of repel-lent activity after application.
The present invention provides a composition having enhanced residual insect repellent activity 20 comprising at least one volatile insect repellent; char-acterized by the composition including at least one polymer consisting of about 49-60 mole percent maleic anhydride and about 51-40 mole percent of at least one l-alkene having 4-30+ carbon atoms, wherein the weight 25 ratio of insect repellent to polymer is from about 10:1 to 50:1 The compositions of the present invention unexpectedly prolong residual activity by reducing skin absorption and evaporation of the insect repellent.
It has been found that the compositions of the invention unexpectedly produce better repellency, i.e., they prolong the protection Crom mosquitoes and flies as compared with those formulations not containing a polymer of the invention.
It has also been unexpectedly found that the addition of a maleic anhydride/alpha olefin polymer to the insect repellent, deet, not only improves residual ~ 3~
activity, but also the tactile characteristics o~ the deet formulation as applied to the skin.
The preferred embodiments of the invention will now be described in detail. The volatile insect re-5 pellents that may be utilized in accordance with theteachings of this invention are those considered ef-fective against the particular insect targeted, and preferably, those compatible with the skin for topical applications.
Examples of volatile insect repellents ef-fective against mos~uitoes and biting flies include:
N,N-diethyl toluamide (deet); ethyl hexanediol; 2-(octyl thio) ethanol; dimethyl phthalate; di-n-propyl-2,5-pyridine dicarboxylate; 1,5a,6,9,9a,9b-hexahydro-15 4a(4h)-dibenæofuran carboxaldehyde; citronellal (3,7-dimethyl-6-octenal); citronellol (3,7-dimethyl-6-octen-1-ol); geraniol (trans-3,7-dimethyl-2,6-octadien-1-ol); nerol (c -3,7-dimethyl-2,6-oct-adien-l-ol); linalool (3,7-dimethyl-1,6-octadien-3-01);
20 and mixtures thereo~.
The concentration of repellent utilized in ac-cordance with the teachings of this invention is not critical. The lower limit is defined by that amount required to form an effective dosage, and the upper 25 limit, by economic considerations. The amount of insect repellent employed will vary depending on several fac-tors, including, the type of insect repellent, the targeted insect or insects, and the other ingredients utilized, e.g., the maleic anhydride polymer.
The concentration of insect repellent can preferably be from about i% to 90~, based on the total weight of the insect repellent composition. The pre ferred ranges are from about 1 to 25 percent, base on the total weight of the insect repellent composition.
35 Unless otherwise indicated, all percen-tages of in-gredients are calculated as weight percentages based on the total weight of the insect repellent compo-sition.
Other insect repellents, especially those well known in the art and useful for such purposes, can also 5 be readily utilized.
Maleic anhydride/alpha olefin polymers may be utilized, in accordance with the teachings of this in-vention, to increase insect residual activity. These polymers include compositions having (a) about 49 to 10 60 mole percent maleic anhydride and (b) about 51 to 40 mole percent of at least one l-alkene having from 4-30+
carbon atoms. Preferred maleic anhydride polymers have (a) about 49-55 mole percent maleic anhydride and (b) about ~5-51 mole percent of at least one l-alkene having 15 from 6-16 carbon atoms, with 8-12 carbon atoms being more preferred. A more preferred polymer has about 50 mole percent maleic anhydride and about 50 mole percent 1-decene.
Additional polymers that may be utilized in ?0 accordance with the teachings of this invention include the maleic anhydride/alpha olefin terpolymers disclosed in U.S. Patent No. 4,358,573. These are formed from monomers comprising: (a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of a least one 25 l-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one l-alkene having from 18-30~ carbon atoms.
Additionally, preferred maleic anhydride/alpha olefin polymers include: (a) about 49 to 55 mole per-30 cent maleic anhydride, (b) about 20 to 30 mole percentof at least one l-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of at least one l-alkene having from 18-24 carbon atoms; and also (a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole 35 percent of at least one 1 alkene havin~ from 8 12 car-bon atoms, and (c) about 20-30 mole percent of a mixture ~ 3~3 of l-alkenes consisting of about ~5-55 mole percent l-eicosene, about 40-55 mole percent l-docosene, and about 5-10 mole percent l-tetracosene.
The maleic anhydride/alpha olefin polymers are 5 generally present in amounts sufficient to reduce the evaporation and skin absorption of the ;nsect repe]lent.
Accordingly, these materials may be present in amounts from about 0.1 to 25 percent, based on the total weight of the insect repellent cornposition, with preferred 10 amounts ranging from about 1 to 5 percent.
It has been discovered, however, that the concentration of polymer is dependent on the concen-tration of insect repellent. Accordingly, a weight ratio of insect repellent to polymer from about 10:1 15 to 50:1 is desirable to attain the objectives of this invention. A weight ratio of 15:1 to 25:1 is more pre-ferred. The particular ratio selected is of course, dependent on the repellent, its volatility and the poly-mer utilized. If the ratio of repellent to polymer is 20 less than about 10:1, the polymer may tightly bind the volatile repellent, thereby preventing its release and repellent effect. If the ratio is greater than about 50:1, the repellent will usually be released too rapidly and the composition will rapidly lose its residual ac-25 tivity.
The application of these compositions is fac-ilitated by solution of the active ingredients in sol-vents, such as the lower alkanols, ethanol and the like, kerosene and similar petroleum oils, ethers, ketones, 3~ aldehydes and the like.
Additionally, the compositions of the pres-ent invention may be applied in aerosol form, in which case, the above-identified compositions may additionally contain a propellent or a mixture of propellents. The 35 type of propellent is not critical and any of those conventionally utilized can be employed to produce an aerosol formula. Typical propellents include isobutane, , 6 -propane, n-butane, and the like, and mixtures thereof, which are utilized in conventional amounts.
In preparing the compositions of -this invention, the insect repellent is generally added directly to an 5 alcoholic polymer solution which can then be formulated ox packaged in any form commonly used for such repellents, i.e., aerosol, pump spray, roll-on or lotion. It is clear to those skilled in the art that the anhydride group of the polymer is converted to the half alkyl 10 ester under these conditions, i.e., the presence of alcohol at room temperature.
In each of the following formulations, MAN=
maleic anhydride. The number or numerical range pre-ceding MAN is the mole percent of maleic anhydride in 15 the polymer. The group Cx Cx, denotes the nu~er of carbon atoms comprising the l-alkene. The number or numerical range preceding this designation is the mole percent of the l-alkene in the polymer.
Typical preparations of this invention 20 include:
~ 3~3 General Formula Amount (percent b~ weight) Ingredients Preferred More Preferxed Insect repellant l-90 1-25 Polymer 0.1-25 0.1-1.5 5 Carrier/propellant 0-99 73.5-99 Repellent:
Formula l Polymer Ingredien-ts Amount ~ by wt.) Ratio Deet 5-50 10:1 to 10 49-60 MA /51-40 C C 0 5-5 50:1 Carrier/propellent 45-95 Repellent:
Formula 2 Polymer I!ngredients Amount (% b~ wt.) Ratio 15 Deet 10-20 15:1 to 49-60 ~ /51-40 C8-C120.1-2 25:1 Carrier/propellent78-90 Repellent:
Formula 3 Polymer ngredientsAmount (~O by wt.) Ratio 20 Deet 15 15:1 50 MAN/50 ClO
Carrier/propellent 84 Repellent:
Fon~a 4 Pol~
IngredientsPmount (~O by wt.) Ratio 25 Deet 5-50 lO:l to 49-55 ~ /20-30-,c8-cl2 o. 5_5 50:1 Carrier/propellent 3''3'~
Repellent Formula 5 Polymer Ingredients Amount (% by wt.) Ratio Deet 10-20 15:1 to 5 49-55 MAN/20-30 C8-C12 0.1-2 25:1 Carrier/propellent 78-90 ~pellent:
Formula 6 Polymer 10 Ingredients Amount (% by wt.) Ratio Deet 15 15:1 Carrier/propellent84 Repellent:
Formula 7 Polymer IngredientsAmount(% by wt.) Ratio -Deet 5-50 10:1 to 49-55 MA /20-30 C8~C12 0.5-5 50:1 Carrier/~ropellent45-95 ~pellent:
Formula 8 Polymer IngredientsAmount ~% by wt.) Ratio 25.Deet ~ 10-20 15;1 to 49-55 MAN/20-30 C8-C12 0.1-2 25:1 20-30 C20-c2~-*/ '78-90 39~
Repellent:
Fo rmul d 9 Po lymer lngre~ients Amount (~ _t.) Ratio Deet 15 15:1 25 C20 C24**/
Carrier/propellent 84 */ The C20-C24 l-alkenes comprise 45-55 mole percent C20, 40 50 mole percent C22 and 5-10 mole percent c24.
**/ The C20-C24 l-alkenes comprise 50.1 mole percent C20, 43.4 mole percent C22 and 6.5 mole percent Fepellent:
15 Formula 10 Polymer In~redients Amount (~ by wt.) Ratio Deet 10-20 15:1 49-55 MAN/20-30c8-l2 0.1-2 20 Carrier/propellent 78-90 In order to illustrate the improved results obtained from the present invention, repellency tests were conducted to show the improvements in residual activity provided by the volatile insect repellent com-25 positions of the present invention. These testsl whichillustrate the scope of the invention but do not limit it, were carried out in the following manner:
The compositions of this invention having the formulations set forth in Table 1 were prepared by mixing an alcohol solution of the polymer with deet and a pro-5 pellent consisting of 75~ isobutane and 25% butane, andpackaging this formulation in standard aerosol cans.
The formulations were tested for their residual repellent activity against mosquit~es and flies for lands and bites as follows: the test insects were 10 adults, reared on 10% sucrose solutions, consisting of (1) about 6,000 mixed sex stable flies, Stomox s cal-cltrans, three weeks from peak emergence, or (2) about 4,000 mixed sex mosquitoes, Aedes aegypti, seven days from peak emergence, that were separately placed in screened 15 wooden cages. A test subject's forearm was thoroughly cleaned, treated with khe repellent material at a rate of 1 gram or 2 ml per 645 square cm. from the wrisk to the elbow, and then exposed to the test insects at pre-determined time intervals, usually one minute every 30 20 minutes, with the first exposure at 30 minutes after application. The observations noted were for repel-lency (no landing insects), lands (insect lands, but does not bite), and bites (insect lands and bikes).
The test was terminated when inseck bites were received 25 during two consecutive exposures. The longer the period between application and the time of first land and/or first bite, the more effective the insect repellent, i.e., the greater its residual activity.
The results in Table 1 demonstrate that at 30 least about a 10:1 weight ratio of insect repellent to polymer significantly increases the residual activity of the repellent, as measured by the time for the first mosquito or fly bite to occur, when compared to a con-trol formulation not containing a polymer of this invention.
~X~ 39 When the weight ratio deet to polymer was lowered to about 7.5:1, i.e., 15% deet and ~% polymer as in Formula B, the residual activity was somewhat better than a control ~ormulation not containing a 5 polymer of this invention. When the ratio of repellent to polymer was lowered still further to about 5:1 as shown in Formula A, the residual activity was inferior to the residual activity of a control formula not con-taining a polymer. It is believed that with ratios 10 lower than about 10:1, the polymer tightly binds the deet, preventing it from volatilizing, and thereby inhibiting its effectiveness as an insect repellent.
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Claims (30)
1. A composition having enhanced residual insect repellent activity comprising:
(1) at least one volatile insect repellent;
and (2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is from about 10:1 to 50:1.
(1) at least one volatile insect repellent;
and (2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is from about 10:1 to 50:1.
2. A composition according to claim 1, wherein the polymer consists of:
(a) about 49-55 mole percent maleic an-hydride, and (b) about 45-51 mole percent of at least one 1-alkene having from 6-16 carbon atoms.
(a) about 49-55 mole percent maleic an-hydride, and (b) about 45-51 mole percent of at least one 1-alkene having from 6-16 carbon atoms.
3. A composition according to claim 2, wherein the 1-alkene has from 8-12 carbon atoms.
4. A composition according to claim 1, wherein the polymer consists of about 49-55 mole percent maleic anhydride and about 45-51 mole percent of 1-decene.
5. A composition according to claim 1, wherein the polymer consists of:
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30+ car-bon atoms.
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30+ car-bon atoms.
6. A composition according to claim 1, wherein the polymer consists of:
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 car-bon atoms, and (c) about 20-30 mole percent of at least one 1-alkene having from 18-24 carbon atoms.
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 car-bon atoms, and (c) about 20-30 mole percent of at least one 1-alkene having from 18-24 carbon atoms.
7. A composition according to claim 1, wherein the polymer consists of:
(a) about 49-55 mole percent maleic an-hydride, (b) about 20-30 mole percent 1-decene, and, (c) about 20-30 mole percent 1-octadecene.
(a) about 49-55 mole percent maleic an-hydride, (b) about 20-30 mole percent 1-decene, and, (c) about 20-30 mole percent 1-octadecene.
8. A composition according to claim 1, wherein the polymer consists of:
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of a mix-ture of 1-alkenes consisting of about 45-55 mole percent 1-eicosene, about 40-55 mole percent 1-docosene, and about 5-10 mole percent 1-tetracosene.
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of a mix-ture of 1-alkenes consisting of about 45-55 mole percent 1-eicosene, about 40-55 mole percent 1-docosene, and about 5-10 mole percent 1-tetracosene.
9. A composition according to claim 1, wherein the volatile insect repellent is selected from the group consisting of N,N-diethyl toluamide; ethyl hexanediol;
2-(octyl thio) ethanol; dimethyl phthalate; di-n-propyl-2,5-pyridine dicarboxylate; 1,52, 6,9, 92, 9b-hexahydro-4a(4h)-dibenzofuran carboxaldehyde; citronellal; cit-ronellol; geraniol; nerol; linalool; and mixtures thereof.
2-(octyl thio) ethanol; dimethyl phthalate; di-n-propyl-2,5-pyridine dicarboxylate; 1,52, 6,9, 92, 9b-hexahydro-4a(4h)-dibenzofuran carboxaldehyde; citronellal; cit-ronellol; geraniol; nerol; linalool; and mixtures thereof.
10. A composition according to claim 1, wherein the insect repellent is N,N-diethyl toluamide.
11. A composition according to claim 1, wherein the volatile insect repellent is N,N-diethyl toluamide and the polymer consists of about 50 mole percent maleic anhydride and about 50 mole percent 1-decene.
12. A composition having enhanced residual insect repellant activity comprising:
(1) at least one volatile insect repellent;
(2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is from about 10:1 to 50:1; and (3) a lower alkanol.
(1) at least one volatile insect repellent;
(2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is from about 10:1 to 50:1; and (3) a lower alkanol.
13. A composition according to claim 12, wherein thepolymer consists of:
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30 carbon atoms.
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30 carbon atoms.
14. A composition according to claim 1, fur-ther comprising a solvent.
15. A composition according to claim 1, fur-ther comprising a propellent.
16. A method for repelling insects which com-prises applying a volatile insect repellent composition to the area to be made repellent, said composition having enhanced residual repellent activity comprising:
(1) at least one volatile insect repellent; and (2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic an-hydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is about 10:1 to 50:1.
(1) at least one volatile insect repellent; and (2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic an-hydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is about 10:1 to 50:1.
17. A method according to claim 16, wherein the polymer consists of:
(a) about 49-55 mole percent maleic anhydride, and (b) about 45-51 mole percent of at least one 1-alkene having from 6-16 carbon atoms.
(a) about 49-55 mole percent maleic anhydride, and (b) about 45-51 mole percent of at least one 1-alkene having from 6-16 carbon atoms.
18. A method according to claim 17, wherein the 1-alkene has from 8-12 carbon atoms.
19. A method according to claim 16, wherein thepolymer consists of about 49-55 mole percent maleic anhydride and about 45-51 mole percent of 1-decene.
20. A method according to claim 16, wherein the polymer consists of:
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30+ carbon atoms.
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30+ carbon atoms.
21. A method according to claim 16, wherein the polymer consists of:
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of at least one 1-alkene having from 18-24 carbon atoms.
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of at least one 1-alkene having from 18-24 carbon atoms.
22. A method according to claim 16, wherein the polymer consists of :
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent 1-decene, and (c) about 20-30 mole percent 1-octadecene.
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent 1-decene, and (c) about 20-30 mole percent 1-octadecene.
23. A method according to claim 16, wherein the polymer consists of:
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of a mixture of 1-alkenes consisting of about 45-55 mole percent 1-eicosene, about 40-55 mole percent 1-docosene and about 5-10 mole percent 1-tetracosene.
(a) about 49-55 mole percent maleic anhydride, (b) about 20-30 mole percent of at least one 1-alkene having from 8-12 carbon atoms, and (c) about 20-30 mole percent of a mixture of 1-alkenes consisting of about 45-55 mole percent 1-eicosene, about 40-55 mole percent 1-docosene and about 5-10 mole percent 1-tetracosene.
24. A method according to claim 16, wherein the volatile insect repellent is selected from the group consisting of N,N-diethyl toluamide; ethyl hexanediol; 2-(octyl thio) ethanol; dimethyl phthalate; di-n-propyl-2,5-pyridine dicarboxylate; 1, 52, 6, 9, 92 9b-hexahydro-4a(4h)-dibenzofuran carboxaldehyde; citronellal;
citronellol; geraniol; nerol; linalool; and mixtures thereof.
citronellol; geraniol; nerol; linalool; and mixtures thereof.
25. A method according to claim 16, wherein the insect repellent is N,N-diethyl toluamide.
26. A method according to claim 16, wherein the volatile insect repellent is N,N-diethly toluamide and the polymer consists of about 50 mole percent maleic anhydrede and about 50 mole percent 1-decene.
27. A method for repelling insects which comprises applying a volatile insect repellent composition to the area to be made repellent, said composition having enhanced residual repellent, said composition having enhanced residual repellent activity comprising:
(1) at least one volatile insect repellent;
(2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is about 10:1 to 50:1; and (3) a lower alkanol.
(1) at least one volatile insect repellent;
(2) at least one polymer consisting of:
(a) about 49-60 mole percent maleic anhydride, and (b) about 51-40 mole percent of at least one 1-alkene having 4-30+ carbon atoms, wherein the weight ratio of insect repellent to polymer is about 10:1 to 50:1; and (3) a lower alkanol.
28. A method according to claim 27, wherein the polymer consists of:
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30 carbon atoms.
(a) about 49-60 mole percent maleic anhydride, (b) about 10-40 mole percent of at least one 1-alkene having from 4-16 carbon atoms, and (c) about 10-40 mole percent of at least one 1-alkene having from 18-30 carbon atoms.
29. A method according to claim 16, further comprising a solvent.
30. A method according to claim 16, further comprising a propellent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2,903 | 1987-01-13 | ||
| US07/002,903 US4774082A (en) | 1987-01-13 | 1987-01-13 | Volatile insect repellents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1281999C true CA1281999C (en) | 1991-03-26 |
Family
ID=21703118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000544473A Expired - Fee Related CA1281999C (en) | 1987-01-13 | 1987-08-13 | Composition and method for repelling insects |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4774082A (en) |
| EP (1) | EP0274574A3 (en) |
| JP (1) | JPS63174902A (en) |
| AU (1) | AU7959187A (en) |
| CA (1) | CA1281999C (en) |
| NZ (1) | NZ221432A (en) |
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| US20070264294A1 (en) * | 2006-05-10 | 2007-11-15 | Lance-Gomez Edward T | Insect control compositions |
| US8114386B2 (en) * | 2006-05-12 | 2012-02-14 | 3M Innovative Properties Company | Topical insect repellent composition and method of application |
| US20080193387A1 (en) * | 2007-02-14 | 2008-08-14 | Ricki De Wolff | Essential oil compositions for killing or repelling ectoparasites and pests and methods for use thereof |
| CA2682179C (en) * | 2007-03-28 | 2013-05-14 | Contech Enterprises Inc. | Allyl sulfide compounds, and compositions and methods using said compounds for repelling blood-feeding arthropods |
| US8231887B2 (en) | 2008-04-11 | 2012-07-31 | Basf Corporation | Pesticidal compositions |
| WO2010099985A2 (en) | 2009-03-05 | 2010-09-10 | Keygene N.V. | Plant volatiles based on r-curcumene |
| ES2397992T3 (en) | 2010-09-15 | 2013-03-12 | Selkis Sas | P-Methane-3,8-diol derivatives and insect repellents that contain them |
| LT3763212T (en) | 2019-07-11 | 2021-12-27 | Sanderstrothmann Gmbh | Arthropoda repellent composition |
| CA3165320A1 (en) | 2020-02-13 | 2021-08-19 | Glycoscience, S.L. | 3'-ketoglycoside compound for the slow release of a volatile alcohol |
| WO2023057235A1 (en) | 2021-10-06 | 2023-04-13 | Glycoscience, S.L. | Process for preparing 3'-ketoglycoside compounds |
| WO2023099327A1 (en) | 2021-11-30 | 2023-06-08 | Glycoscience, S.L. | Slow-release formulation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2884355A (en) * | 1954-08-30 | 1959-04-28 | Phillips Petroleum Co | Insect repellent composition comprising a diethyl, di-n-protyl or di-n-butyl pyridine dicarboxylate, a stabilizer and a method of use |
| US2808359A (en) * | 1957-02-19 | 1957-10-01 | Alfred F Schmutzler | Insect repellent compositions of hydroxy-alkyl esters of polybasic organic acids and methods of using same |
| US3860700A (en) * | 1966-12-08 | 1975-01-14 | Oreal | Certain copolymers and their use in cosmetics |
| US3966902A (en) * | 1972-05-12 | 1976-06-29 | Airwick Industries, Inc. | Polymer complex carriers for an active ingredient |
| US4512969A (en) * | 1974-09-17 | 1985-04-23 | Eastman Kodak Company | Compositions containing hydrophobic addenda uniformly loaded in latex polymer particles |
| DE2658725A1 (en) * | 1976-12-24 | 1978-07-06 | Bayer Ag | AGENT FOR CONTROLLING ANIMAL EECTOPARASITES WITH A STRONG RESIDUAL EFFECT |
| JPS585881B2 (en) * | 1979-03-28 | 1983-02-02 | 日東電工株式会社 | Long-lasting repellent composition |
| US4435383A (en) * | 1980-09-05 | 1984-03-06 | E. I. Du Pont De Nemours And Company | Slow release pesticide formulations |
| US4358573A (en) * | 1981-05-29 | 1982-11-09 | S. C. Johnson & Son, Inc. | Waxy maleic anhydride alpha olefin terpolymers |
| US4657759A (en) * | 1981-07-31 | 1987-04-14 | Nordtend A/S | Method and means for repelling animals |
| US4388352A (en) * | 1981-08-03 | 1983-06-14 | Board Of Regents, University Of Washington | Method for preparing a controlled release composition |
| US4489056A (en) * | 1982-06-30 | 1984-12-18 | Merck & Co., Inc. | Acid anhydrides as rate controlling agent for the erosion of polymers which latter polymers have beneficial substances dispersed throughout their matrix or where the polymer matrix surrounds the beneficial substance |
| US4548764A (en) * | 1983-02-23 | 1985-10-22 | International Flavors & Fragrances Inc. | Insect repellent, pheremonal, animal repellent, diagnostic or aroma enhancing compositions containing poly(epsilon caprolactone) having embedded therein functional substances |
| US4663346A (en) * | 1984-05-30 | 1987-05-05 | Angus Chemical Company | Insect repellent |
| JPS6268728A (en) * | 1985-09-24 | 1987-03-28 | Nippon Petrochem Co Ltd | Preparation of laminated body |
| US4693890A (en) * | 1986-06-27 | 1987-09-15 | International Flavors & Fragrances Inc. | Use of 1-nonen-3-ol for repelling insects |
-
1987
- 1987-01-13 US US07/002,903 patent/US4774082A/en not_active Expired - Lifetime
- 1987-08-12 NZ NZ221432A patent/NZ221432A/en unknown
- 1987-08-13 CA CA000544473A patent/CA1281999C/en not_active Expired - Fee Related
- 1987-10-01 EP EP87114344A patent/EP0274574A3/en not_active Withdrawn
- 1987-10-13 AU AU79591/87A patent/AU7959187A/en not_active Abandoned
- 1987-10-15 JP JP62258472A patent/JPS63174902A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU7959187A (en) | 1988-07-14 |
| US4774082A (en) | 1988-09-27 |
| NZ221432A (en) | 1990-07-26 |
| JPS63174902A (en) | 1988-07-19 |
| EP0274574A2 (en) | 1988-07-20 |
| EP0274574A3 (en) | 1989-06-07 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |