Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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REPELLENT COMPOSITION
FI~LD OF THE INVENTION
This invention relates to a pest repellent composition and
to methods of repelling pests from a substrate, particu-
larly human skin.
BACXGROUND OF THE INVENTION
Various compositions have been used over the years to
repel insects and other pests from humans, pets and other
animals. These compositisns have al~o been used to repel
insects from inanimate ~bjects, such as clothing, furni-
ture and food. Moth balls and citronella oil are examples
of materials which have been widely used as repellents.
In recent years, insect repellents marketed for use on
humans have contained N,N-diethyl-m-toluamide (DEET) as
their active ingredient. USSR Inventor's Certificate No.
733,681, published May 25, 1980, describes a repellent
cream containing DEET, paraffin, ceresine, a fatty base,
a filler and perfume. The Inventor's Certificate also
suggests that the repellent activity of this composition
is increased and its toxicity is decreased when carboxide,
glyceryl monostearate and stearic acid are added to the
repellent cream, but there is no reported experimental
data to substantiate these effects.
While DEET generally provides good efficacy in repelling
insects, it8 odor i8 not particularly pleasing and it has
been reported to irritate the eyes, mucus membranes and
sensitive skin. Issues relating to the toxicity of DEET
in humans have also been raised and the Centers for
.
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Disease Control and other regulatory agencies have issued
cautionary statements relating to the use of DEET.
. .
Other organic compounds have been used as insect repel-
lents. For example, U.s. Patent No. 5,109,022 issued
April 28, 1992 to R.L. Jeanne, et al., describes the use
of methyl myristate, methyl palmitate, butyl palmitate and
combinations thereof as repellents for flying, biting and
stinging insects. Since these compounds are generally
insoluble in water, they are dissolved or dispersed in a
non-polar liquid carrier, or adsorbed onto a solid carri-
er, and then processed into the desired form for use as an
insect repellent. An ointment base, such as mineral oil,
polyethylene glycol and paraffin oils may also be used
with these compounds.
Natural fragrance oils have been shown to possess repel-
lency against certain insects. U.S. Patent No. 5,106,622
issued April 21, 1992 to Kisherwood et al. describes a
repellent composition containing equal amounts of natural
oils of citronella, cedar and wintergreen. These oils are
combined with a non-toxic, oil-based carrier, such as
oleic acid. Pennyroyal oil and the natural oils of
eucalyptus and camphor may also be added to the composi-
tion in small amounts. In addition to the oil form, the
composition may also be formulated as a cream, lotion,
spray or roll-on.
Repellent compositions employing fragrances as the active
ingredients are described in PCT Publication No. W0
91/15118, published October 17, 1991 to D.T. Beldock, et
al. This insect repellent composition contains a cosmetic
moisturizing lotion base and turpenoil, citronella, rhod-
enol extract and geraniol as the insect repelling actives.
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sunscreen actives may also be added to the composition to
provide a multi-purpose lotion. Beldock, et al., also
suggest that water or alcohol may be combined with the
actives to provide an insect repellent spray.
Avon Products, Inc.,'s Skin-So-Soft0 bath oil has been
reported as having repellent activity. While it is widely
thought that the fragrance oils employed in this composi-
tion provide the repellency, G.J. Magnon, et al., in an
article entitled "Repellency of Two DEET Formulations and
Avon Skin-So-Soft~ Against Biting Midges (Diptera Ceratop-
ogonidae) in Honduras", Journal of the American Mosquito
Control Association, Vol. 7, No. 1, pp. 80-2 (1991) report
that Skin-So-Soft bath oil does not appear to repel biting
midges. Rather, it acts as an oily barrier and physically
traps the midges on the sticky surface of the skin.
While repellent compositions containing natural fragrance
oils as the actives avoid many of the health concerns
associated with DEET, they have found only limited use
because of their short-lasting effect. These repellents
generally require reapplication every one to two hours by
the consumer.
In view of the health concerns associated with DEET and
the short-lasting effect of repellent compositions con-
taining natural fragrance oils as the actives, there
exists a need for a safe, longer--lasting repellent compo- `
sition.
8UMMARY OF T~B--~NyE~TIQ~
It has been discovered that the lasting-effect of a
repellent composition containing a fragrance as the active
repellent is substantially enhanced through the addition
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of a fatty acid ester of a polyhydric alcohol. The
repellent composition comprises the aforementioned fatty
acid ester of a polyhydric alcohol, a fragrance having
repelling activity and an extending medium. In a pre-
ferred form of the invention, the fatty acid ester of apolyhydric alcohol is glyceryl oleate and the extending
medium is mineral oil.
Another aspect of the invention is a process for repelling
insects from a substrate which comprises applying to the
substrate the above-described repellent composition.
8RIEF DE8CRIPTION OF ~HE DRAWING8
FIG. 1 and 2 are gas chromatograms of two of the repelling
fragrances used in the present invention.
:. :
DE~AILED DESCRIPTION OF THE PREFERRED EM~ODINENT8
The pest repellent composition of the present invention
contains a fatty acid ester of a polyhydric alcohol which
has ~een shown to increase the lasting-effect of a fra-
grance having pest repelling activity. The lasting-effect
of the composition is from about two to three fold greater
than a composition free of the fatty acid ester of a poly-
hydric alcohol. These compositions overcome the above-
described short comings of repellent compositions contain-
ing fragrances as the active ingredients.
The term "pest" as used in the present invention, includes
insects and other arthropods, such as ticks, known to be
harm~ul or annoying to sub~ect hosts, such as humans, pets
and other domesticated animals. While the repellent
compositions of the present invention are suitable for
topical application to the user's skin, they may also be
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applied to inanimate objects such as clothing and furni-
ture.
The pest repellent composition of the invention comprises
a fatty acid ester of a polyhydric alcohol, a pest repel-
ling fragrance and an extending medium. The fatty acid
ester of a polyhydric alcohol and the pest repelling
fragrance are present in the composition in amounts
sufficient to provide the desired repellency. In one
embodiment of the invention, the composition comprises
about 0.5-20%, preferably about 1-10%, of the fatty acid
ester of a polyhydric alcohol, about O.S-30%, preferably
about 1-10%, of the pest repelling fragrance and about 60-
99%, preferably 80-g5%, of the extending medium, by weight
of the total composition. The weight ratio of fatty acid
esters of a polyhydric alcohol to pest repelling fragrance
is within the range of about 1:10 to 10:1 and preferably
about 2:1 to 1:2. A solubilizing agent in an amount
ranging from about 0-10%, preferably 0.1-10%, and most
preferably about 1-5%, by weight of the total composition,
may also be employed.
The fatty acid esters of a polyhydric alcohol suitable for
use in the present invention are surfactants which are
used in cosmetic and personal care compositions. These
fatty acid esters of a polyhydric alcohol have the formu-
la:
R, -C-O-R2
wherein:
Rl is straight or branched, saturated or unsaturated
aliphatic having about 8 to 22 carbon atoms; and
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R2 is straight or branched, polyhydroxy substituted alkyl
having about 3 to 6 carbon atoms or polyhydroxy substi-
tuted cyclic ether having 5 or 6 members. As used in this
invention polyhydroxy means di- and trihydroxy and members
refers to the oxygen and carbon atoms in the cyclic ether
chain.
Representative fatty acid esters of a polyhydric alcohol
suitable for use in the invention include glyceryl oleate,
sorbitan laurate, mannitan laurate, glyceryl palmitate,
glyceryl stearate, glyceryl arachidate, glyceryl palmito-
leate, glyceryl margarate (C17), glyceryl linoleate,
glyceryl linolenolate, glyceryl ricinoleate, glyceryl
licanate, glyceryl eleostearate, glyceryl octadeca-
tetraenoate, glyceryl nonadecanoate, glyceryl eicosenoate,
glyceryl eicosadienoate, glyceryl arachidoate, glyceryl
eicosapentaenoate, glyceryl isostearate, glyceryl isohexa-
decanoate, glyceryl isoarachidoate, dihydroxy butyl
oleate, dihydroxy pentyl linoleate, trihydroxyl hexyl-
isostearate, sorbitan palmitate, mannitan arachidoate, 2,
methyl,2,4, dihydroxypentyloleate, and pentaerythrityl
oleate.
Preferably, Rl is a straight or branched, unsaturated
aliphatic having about 16 to 20 carbon atoms and R2 is:
-CH2C(H)(OH)CH2OH
~hese surfactants are commercially available from many
supplier~. Preferred fatty acid esters of a polyhydric
alcohol include glyceryl oleate from ICI Americas, Inc.
under the tradename ARLACEL 186 and sorbitan laurate,
available from ICI under the tradename ARLACEL 20.
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ARLACEL 186 is a 90:10 (by weight) mixture~ of glyceryl
oleate and propylene glycol.
The pest repelling fragrance used in the present invention
include substances having an aroma which repels insects
and other arthropods. Included within this class of
fragrances are natural fragrance oils having repelling
activity. Exemplary fragrances include cedarwood, citro-
nella, coumarin, indole, p-hydroxybenzyl acetone, musk,
vanillin, roseacetol, musk ambrette cedrol, ~-terpineol,
linalool, isoborneal, terpineol, geranial, cassia, chamo-
mile, cinnamon, coriander, lavendarj rosewood, sandalwood,
pepperint, anise, clove, citronellal, citronellol and
methyl heptenone. one or more of these pest repelling
fragrances may be used in the composition.
A preferred fragrance oil is Givaudan-Roure's PA73726 and
International Flavors and Fragrances' 1448-AP, both of
which have a mildly floral fragrance. The gas chromato-
grams for these fragrances are shown in FIGS. 1 and 2,respectively.
The extending medium suitable for use in this invention is
a pharmaceutically or cosmetically acceptable carrier or
vehicle which can be combined with the fatty acid ester of
a polyhydric alcohol and the pest repelling fragrance, and
then applied to a substrate, particularly human skin. The
composition of the present invention may take the form of
a cream, lotion, oil, spray, roll-on and other convention-
al repellent forms. Extending medium suitable for use inthe invention include petroleum extenders, such as petro-
latum, mineral oil, and mineral spirits; vegetable derived
oils, such as, coconut, peanut, babassu, palm, palm
kernel, soybean, castor, corn, olive, linseed, oiticica,
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rapeseed, rice bran, safflower, sesame, sorghum, sunflow-
er, tall, and tung; animal derived oils, such as beef
tallow, mutton tallow, tallow yellow grease, hydrogenated
tallow, butterfat, goose grease, poultry, lard, neatsfoot,
and mink; marine derived extenders, such as whale, her-
ring, sperm, and menhadin; synthetic and semi-synthetic
oils such as disopropyl pthalate, myristyl myristate,
isopropyl, myristate, dioctyl pthalate, benyl benzoate, n-
heptyl, heptanoate, neodecanoic acid, n-dodecanol, tri-
decanol stearyl alcohol, isostearyl alcohol, dipropyleneglycol, propylene glycol, glycerine; water; and mixtures
thereof.
The compositions of the present invention may also include
solubilizing agents known to be used in cosmetic and
personal care formulations. Coupling agents are also
included within this class of materials. These agents are
used to promote clarity and stability.
Exemplary solubilizing agents include polyoxypropylene
(15) lauryl ether, and dipropylene glycol polyoxypropylene
(5) isostearyl ether. A preferred solubilizing agent for
use in the present invention is polyoxypropylene (10)
stearyl ether sold by ICI Americas, Inc. under the trade-
name ARLAMOL F.
~he compositions of the present invention may also containother ad~uvants, commonly used in cosmetic and personal
care formulations. For example, if the composition should
also render protection against the sun, known sunscreen
agents, such as para-amino benzoic acid and derivatives
thereof, oxybenzones, methoxycinnamates titanium dioxide
and zinc oxide may be added.
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Compositions of the present invention may be prepared
using techniques known in the art. During such prepara-
tion, emulsifying agents, suspending agents, penetrants,
wetting agents, tackifiers, stabilizers, and thickening
agents may be added to the repellent composition.
.
The repellent composition is applied to the substrate in
virtually any manner so long as the fatty acid of a
polyhydric alcohol and the pest repelling fragrance remain
deposited on the surface. Such applications may include
rubbing, spraying, painting, dipping or other techniques
known in the art. If a non-volatile extending medium is
employed, it will also remain deposited on the substrate
surface with the extending medium and the pest repelling
fragrance.
Speci~ic embodiments of the present invention are illus-
trated by way of the following examples. This invention
is not confined to the specific limitations set forth in
these examples, but rather to the scope of the appended
claims.
~.'.
FXAMPLE
The compositions shown below were prepared by mixing the
ingredients in the stated proportions in a vessel with a
stirrer.
Sample ~%W/W)
A* B
naredients
Fragrance Oil 6.0 6.0
(Givaudan-Roure PA73726)
Glyceryl Oleate~ - 3.0
(ARLACE~ 186)
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Mineral Oil 94 . O 91. 0
Comparative
~ Contain 10% (by wt.) propylene glycol
Samples A and B were tested for their repellency on human
volunteers using the following cage test:
Equipment
Test Chambers:
One aluminum cage 2 x 2 x Z foot square with two
sleeved entry ports at opposite ends of the cage. The
bottom was equipped with a mirror to facilitate observa~
tion and a hand rest was provided in the center.
~est Oraanism:
Five hundred female Aedes aeaypti mosquitoes were
released in the test cage prior to the beginning the
study. The mosquitoes were taken off sucrose twenty four
hours prior to their utilization in the study.
~est Subiects:
Human volunteers were used as the test subjects. In
preparation for the study, they washed their arms with
Ivory soap. They wore short sleeved shirts and had the
skin above and below the target area (250 cm2 area),
protected with elastic ACE bandages held in place-with
i~urgical tape. The hands were protected with surgical
gloves.
Procedures
Each test sub~ect was prepared as described above.
Each test sample was applied to ~our separate test sites.
A single test site consisted of the test subject's fore-
arm. The repellent was applied at the rate of 1 ml per
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250 cm2 area. Each test subject's forearm was allowed to
air dry for 30 minutes prior to the first exposure. Each
exposure duration was for 5 minutes and the test subjects
were then re-exposed at thrity minute intervals until the
first confirmed bite.
The test recorder, prior to assisting the test
subjects into the arm ports, exposed his untreated arm to
confirm biting aggressiveness. Bites (blood is ingested,
as evidenced by abdominal swelling and color change) and
probes (mosquito attempts to imbed the mouth parts) were
recorded. When a confirmed bite` occurred on an arm,
testing was discontinued on that arm. A confirmed bite
was a bite followed by another bite in the same exposure
period or in the following exposure period. The time of
the first confirmed bite was recorded for each of the four
test sites and the sample protection time is reported
below as the average of these four recorded times.
The results of the experiment are as follows:
Sample Protection Time Versus A.Aegepti
A 1.9 hours
B 3.3 hours
These results demonstrate that when the insect repelling
fragrance is used in the composition of the present
invention containing glyceryl oleate, the protection time
increases by greater than 70%.
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EXAMPLE II -: -:
The compositions shown below were prepared by mixing the
ingredients in the stated proportions using procedures
similar to those described in Example I.
Sample (%W/W)
A* B* C
Inaredients
Fragrance Oil 12.0 - 6.0 -
(Givaudan-Roure PA73726) ~
Glyceryl Oleate~ - 12.0 6.0 ~ ~ ;
(ARLACEL 186) ~
. .
Mineral Oil 88.0 88.0 88.0
Comparative
~ Contains 10% (by wt.) propylene glycol
Samples A, B and C were tested for their repellency
against female A. Aegepti mosquitos using the procedure
described in Example I. The results of the experiment are
as follows:
~m~le Protection Time Versus A.Aeaepti
A 3.5 hours
B 3.0 hours
C 7.5 hours ~ ~i
The above results demonstrate that the compositions of the
present invention containing the fragrance oil and glycer-
yl oleate (Sample C) exhibits synergistic repellency
activity, when compared to the compositions containing the
fragrance oil (Sample A) and glyceryl oleate (Sample B)
alone.
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EXAMPLE III
The compositions shown below were prepared by mixing the
ingredients in the stated proportions using procedures
similar to those described in Example I.
Sample (~W/W)
A* B* C
Inaredients
Fragrance Oil - 12.0 6.0
(Givaudan-Roure PA73726)
Sorbitan Laurate 12 - 6.0
(ARLACEL 20)
Mineral Oil 88.0 88.0 88.0
*Comparative
Samples A, B and C were tested for their repellency
against female A. Aegepti mosquitos using the procedure
described in Example I. The results of the experiment are
as follows:
Sample Protection Time Versus A. Aegepti
A 2.0 hours
B 2.13 hours
C 3.25 hours
The above results show that the protection time increases
with the composition of the present invention containing
sorbitan laurate and the fragrance (Sample C), when
compared to compositions containing sorbitan laurate
(Sample A) or the fragrance (Sample B) alone.
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EXAMPLE IV
The compositions shown below were prepared by mixing the
ingredients in the stated proportions using the procedures -
similar to those described in Example I.
S
Sample (%w/W)
A B ~ `
Inaredients - :
Fragrance Oil 6.0 6.0
(Givaudan-Roure PA73726)
-~ ,
Glyceryl Oleatel 6.0 6.0 ~ .
(ARLACEL 186)
Sorbitan Laurate 2.0 2.0
(ARLACEL 20)
Polyoxypropylene (10) :
Stearyl Ether 2.0 2.0
(ARLAMOL F)
",?
Citronella Oil 0.1
Mineral Oil 83.9 84.0
Contains 10% (by wt.) propylene glycol
Samples A and B were tested for their repellency using the
procedure described in Example I, except that biting flies
(Stomoxys Calcitrans) were substituted for mosquitoes.
The average results of the experiment are as follows:
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Sample Protection Time Versus ~. Calcitrans
A 4.75 hours
B 3.0 hours
The above results demonstrate that the compositions of the
invention (Samples A and B) exhibit excellent repellency
to biting flies.
EXAMPL~ V
Sample B of Example IV was tested for its repellency
against ticks (Ixodes Dammini) under field conditions
using a drag test. Approximately 7.5 ml of Sample B was
sprayed, in nine even sw~eping motions, over each side of
a 2 x 3 foot white cotton flannel rectangle. The control
was an untreated rectangle.
The drags were slowly pulled a distance of 50 meters over
a tick infested area consisting of grass and low bushes
and then placed in a bag and sealed. The sealed bags were
placed in a freezer overnight to kill all the ticks before
counting. The following summarizes the count results:
Drag
Treated Control
Total No. of Drags Tested 56 14
No. of Tick-free Drags 21 2
Total Nymphs Recovered 54 38
Av. Nymphs per Drag 0.96 2.71
Total Larvae Recovered 9 3
Avg. Larvae per Drag 0.16 0.21
The re6ults demonstrate that significantly fewer ticks
were recovered from the drag treated with the composition
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of the present invention as compared to the untreated
drags. The composition of this invention, therefore, has
been shown to exhibit repellency to ticks and can be used
on inanimate objects.
EXANPLE VI
The composition shown below, containing sunscreen actives,
was prepared using the procedures similar to those de-
scribed in Example I. ~ -
' '
Inqredient % W/W
Fragrance Oil 6.0
(Givaudan-Roure PA 73726)
Glyceryl Oleate~ 6.0
(ARLACEL 186)
Sorbitan Laurate 2.0
(ARLA OE L 20)
Oxybenzone 3.0
Octyl Methoxycinnamate 7.5
Mineral Oil 75.5
~ Contains 10% (by weight) propylene glycol.
Using the procedure described in Example 1, the above
composition had a protection time of seven hours against
A. Aegepti mosquitoes. The sun protection factor for this
composition was SPF 12 test (Sun Protection Factor) using
a ~tandard in-vitro SPF method.
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2111909
EXAMPLE VII
A water-in-oil (w/o) sunscreen lotion containing titanium
dioxide and zinc oxide, as the sunscreen actives, was
prepared using conventional techniqus. The ingredients
listed below were then mixed with the lotion in the stated
proportions.
Sample (%W/W)
A B
Inaredients
W/O Sunscreen Lotion 86.0 86.0
Sorbitan Laurate 2.0 2.0
Glyceryl Oleate~ 6.0 6.0
(ARLACEL 186)
Fragrance Oil
Givaudan-Roure PA73726 6.0
IFF 1448-AP - 6.0
. .
~ Contains lOS ~by wt.) propylene glycol
Samples A and B were tested for their repellency against
A. Aegepti mosquitoes using the procedures described in
Example I. The results of their experiment are as fol-
low~:
Sam~le Protection Time Versus A. Aeae~ti
A 3.9 hours
B 4.3 hours
The above results demonstrate excellent repellency using
two different pest repelling fragrances. These composi-
tions are also effective sunscreen lotions.
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E~MPLE VIII
Givaudan-Roure Fragrance PA 73726 and IFF Fragrance 1448- -
AP were each dissolved in methanol (1:20), and 1 microli-
ter sample was injected into a gas chromatograph-mass ~ '
spectrometer under the following chromatographic condi-
tions:
Column: DB-WAX, 0.5 ~m, 30 m
Injector Temp: 225C
Split: 1:15
Initial Temp: 80C
Initial Hold Time: 2 min.
Heating Rate: 8C/min.
Final Temp: 220C
Final Hold Time: 15 min.
:. :.:
The resulting chromatograms for the Givaudan Fragrance is
shown in Figure 1. The six ma~or peaks at scan numbers
215, 306, 378, 471, 694 and 775 were computer searched in
a spectral library based on EI fragmentation and the
results are shown below:
~ '' '.'' '
Eç~n Structure Purity*
215 5-Hepten-2-one, 6-methyl 941
306 Bicyclo[2.2.1]heptan-2-ol, 770
1,7,7-trimethyl-,formate, endo- ~
' ~; "
378 2-Cyclohexene-1-methanol, 860
alpha, alpha, 4-trimethyl-,
471 Benzeneethanol 934
;''.',''
694 1,2-Benzenedicarboxylic 962
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acid, Diethyl ether
775 2H-1-Benzopyran-2-one 739
* The higher the purity (max.= looo), the better the match
of the spectrum.
The resulting chromatogram for the IFF Fragrance is shown
in Figure 2. The three major peaks at scan numbers 309,
344 and 601 were computer searched on a spectral library
based on EI fragmentation and the results are shown below:
Scan Structure ` Purity*
309 Bicycylo [2.2.1] heptan-2-ol,
1,7,7-trimethyl-, formate, endo- 810
344 Ethanol, 2-[2-(2-ethoxyethoxy)
ethoxy]- 761
601 Benzoic Acid, 2-Hydroxy-,
Phenylemethyl Ester 885
* The higher the purity (max.= 1000), the better the match
oi the spectrum.
Various modifications, can be made to the above described
embodiments without departing from the spirit and scope of
the present invention.
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