Title: Non-ethanol perfume compositions comprising hydrofluoroether

Date: 09/16/2008

Applicants:
Name:
Souvie Marie-Laure
City:
Orléans
State:
Country:
FR
Assignees:
Organization Name:
LVMH Recherche
City:
Paris
State:
Country:
FR
Abstract:
The invention relates to an ethanol-free or alcohol-free composition.This ethanol-free
or alcohol-free composition comprises a hydrofluoro ether and is characterized in that
it comprises at least one ester of a polyacid, preferably a hydroxylated polyacid.This
composition can be used in the preparation of perfume compositions such as perfumes
and toilet waters.
Claims:

 1. A perfume composition free of ethanol or alcohol, comprising a perfume

concentrate comprising at least one essential oil, and a solubilizer comprising an
association of a hydrofluoro ether component and of at least one polyacid ester in an
amount sufficient to give said composition an essentially clear appearance.
 2. The composition of claim 1, wherein the hydrofluoro ether component is selected
from the group consisting of methoxynonafluorobutane, ethoxynonafluorobutane,
propoxyundecafluoropentane and methoxyheptafluoropropane.
 3. The composition of claim 1, wherein the polyacid ester is an ester of a hydroxylated
or non-hydroxylated polyacid esterified with a saturated or unsaturated, linear or
branched alcohol having between 1 and 30 carbon atoms.
 4. The composition of claim 1, wherein the polyacid ester is an ester of a polyacid
with an alcohol having between 1 and 12 carbon atoms.
 5. The composition of claim 1, wherein the polyacid ester is an ester of a polyacid
with an alcohol selected from the group consisting of ethanol, isopropanol and 2-
ethylhexanol.
 6. The composition of claim 1, wherein the polyacid has between 3 and 10 atoms and
comprises a linear or branched, saturated or unsaturated carbon chain optionally
substituted by at least one substituent selected from the group consisting of hydroxyl,
ketone, and hydroxyl substituted by acetyl.
 7. The composition of claim 1, wherein the polyacid is a total ester of a polyacid with
a saturated or unsaturated, linear or branched alcohol having between 1 and 30 carbon
atoms.
 8. The composition of claim 1, wherein the polyacid is a saturated diacid selected
from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, suberic acid and azelaic acid; a monounsaturated diacid selected from
the group consisting of fumaric acid, maleic acid, citraconic acid, itaconic acid and
mesaconic acid; a diunsaturated diacid; muconic acid; a monohydroxylated diacid;
tartronic acid; malic acid; citramalic acid; a dihydroxylated diacid; dihydroxymaleic;
tartaric acid, a tetrahydroxylated diacid; dihydroxytartaric acid; galactaric acid;
glucaric acid; a keto diacid; mesoxalic acid; oxalacetic acid; 2-oxoglutaric acid; 3-
oxoglutaric acid, a diketo diacid; 2,3-diketoadipic acid, a saturated triacid;
tricarballylic acid; citric acid, an unsaturated triacid; and aconitic acid.
 9. The composition of claim 1, wherein the polyacid is citric acid.
 10. The composition of claim 1, wherein the polyacid is adipic acid.
 11. The composition of claim 1, wherein the polyacid ester is a substantially non-polar
ester.
 12. The composition of claim 1, wherein the polyacid ester is selected from the group
consisting of triethyl citrate, tri(2-ethylhexyl) citrate, diisopropyl adipate and di(2-
ethylhexyl) adipate.
 13. The composition of claim 1, wherein the polyacid ester represents from 0.1 to
30% by weight of the hydrofluoro ether component.
 14. The composition of claim 1, wherein the polyacid ester represents from 1 to 20%
by weight of the hydrofluoro ether component.
 15. The composition of claim 1, further comprising a silicone selected from a volatile
silicone, a dimethicone, a cyclomethicone, pentacyclomethicone, and an
organotrisiloxane, the silicone representing from 1 to 20% by weight of the
composition.
 16. The perfume composition of claim 1, wherein the hydrofluoroether component is
present in an amount ranging from about 65 to about 85% by weight, based on the
weight of the perfume composition.
 17. The composition of claim 16, comprising from about 1 to about 20% by weight of
polyacid ester, based on the weight of the perfume composition.
 18. The composition of claim 1, comprising from about 5 to about 20% by weight of
 perfume concentrate.
 19. The composition of claim 1, formulated as a body lotion comprising a
concentration of perfume concentrate in the order of 5% by weight, based on the
weight of the composition.
 20. The composition of claim 1, formulated as a perfume, the concentration of
perfume concentrate being between 10 and 20% by weight of the perfume
composition.
 21. The composition of claim 1, wherein the hydrofluoro ether component is a
perfluorinated component of the general formula CnHmFp—O—CxHyFz, in which n
is a number ranging from 1 to 12, m is a number ranging from 0 to 25, p is a number
ranging from 0 to 11, m+p=2n+1, x is a number from 1 to 12, y is a number from 0 to
25, x is a number from 0 to 11 and y+z=2x+1, and in which m and y may not be equal
to 0 simultaneously and p and z may not be equal to 0 simultaneously.
 22. The composition of claim 1, comprising an additional component, selected from a
second co-solvent, and from a component for improving the properties of the perfume
composition.
 23. The composition of claim 22, wherein the second co-solvent is a silicone and
wherein the component for improving the properties of the perfume composition is
promoting the persistence of said composition on the skin, and comprises a phthalate.
 24. The composition of claim 23, wherein said phthalate is diethyl phthalate.
 25. The composition of claim 1, further comprising up to 2% by weight, based on the
composition, of at least one additional additive including a UV filter, an antioxidant or
a dye.
 26. A method of solubilizing an alcohol-free and ethanol free perfume concentrate
comprising admixing the perfume concentrate comprising at least one with a
solubilizer comprising an association of comprising a hydrofluoroether component
and a polyacid ester, thereby obtaining the perfume composition of claim 1.
 27. The method of claim 26, wherein the hydrofluoro ether component is a
perfluorinated component of the general formula CnHmFp—O—CxHyFz, in which n
is a number ranging from 1 to 12, m is a number ranging from 0 to 25, p is a number
ranging from 0 to 11, m+p=2n+1, x is a number from 1 to 12, y is a number from 0 to
25, x is a number from 0 to 11 and y+z=2x+1, and in which m and y may not be equal
to 0 simultaneously and p and z may not be equal to 0 simultaneously.
 28. The method of claim 26, further comprising preparing a perfume composition
selected from a perfume and a body lotion.
 29. An ethanol-free or alcohol-free perfume composition, comprising a perfume
concentrate comprising at least one essential oil, and a solubilizer comprising an
association of a, hydrofluoro ether component selected from the group consisting of
methoxynonafluorobutane, ethoxynonafluorobutane, propoxyundecafluoropentane
and methoxyheptafluoropropane, and a polyacid ester selected from the group
consisting of triethyl citrate, tri(2-ethylhexyl) citrate, diisopropyl adipate and di(2-
 ethylhexyl) adipate.
 30. The composition of claim 29, further comprising a silicone selected from a
volatile silicone, a dimethicone, a cyclomethicone, pentacyclomethicone, and an
organotrisiloxane, the silicone representing from 1 to 20% by weight of the
composition.

Description:

 The invention relates essentially to a non-ethanolic composition comprising a

perfluorinated hydrofluoro ether and at least one co-solvent, other than water and
ethanol, comprising a polyacid ester, and to its use in perfume compositions.
 Such perfume compositions are preferably ethanol-free perfume compositions of
which all the components are miscible with one another to give the composition the
appearance of a clear liquid.
 In perfume products (perfume, toilet water, etc.), the presence of alcohol (ethanol),
which is used mainly as a solubilizer for the perfume concentrate, presents a number
of problems well known to those skilled in the art. It is for this reason that research
has been carried out for many years on perfume products which avoid the addition of
alcohol by replacing it with other solubilizers.
 As examples, reference may be made to the documents WO 99/18925 and U.S. Pat.
No. 5,468,725, which describe alcohol-free perfume compositions and respectively
use silicones as solubilizer and the microemulsion technique.
 One of the general problems which arise is the olfactory preservation of the perfume
concentrate composition and especially the olfactory neutrality of the solubilizers
used.
 Furthermore, the document WO 99/11225 discloses cosmetic preparations in which
the essential ingredients are at least 1% of hydrofluoro ether for the purpose of
improving the tolerability of these compositions on the skin and improving the feel of
the cosmetic product.
 Also, the document WO 99/26600 discloses the use of perfiluorinated hydrofluoro
ethers as agents for dissolving aromatic compounds in the preparation of a cosmetic
composition. On page 3, lines 21 to 25, said document envisages in general terms the
possibility of adding at least one co-solvent, which is indicated as preferably being
selected from the group comprising ethanol and water, i.e. in practice an aqueous-
alcoholic mixture. The Examples given in said document all relate to the exclusive use
of a hydroperfluoro ether for solubilizing essential oils. The hydroperfluoro ethers
mentioned are methoxynonafluorobutane, abbreviated to MNFB, in Examples 1 and
2, ethoxynonafluorobutane, abbreviated to ENFB, in Examples 3 to 8, and also
propoxyundecafluoropentane.
 A specific problem exists with perfume compositions, namely the necessary solubility
of all the constituents of such a perfume composition. A principal component is made
up of a perfume concentrate containing essential oils together with various
 components such as emulsifiers or surfactants, fatty esters or cellulose derivatives,
together with other components well known to those skilled in the art.
 In the context of experiments performed with a view to obtaining ethanol-free or
alcohol-free compositions, the Applicant performed experiments aimed at verifying
whether perfluorinated hydrofluoro ethers were capable on their own of totally
solubilizing such perfume concentrates in order to prepare perfume compositions,
these perfume concentrates being commercially available and marketed by companies
specialized in their manufacture, such as GIVAUDAN, Switzerland, FIRMENICH,
Switzerland, or International Flavors & Fragrances (IFF), USA. Now, all the
experiments turned out negative in the sense that the liquids obtained were not clear
but were obviously made up of two distinct phases.
 One main object of the present invention is thus to solve the novel technical problem
consisting in the provision of a solution which makes it possible to prepare
compositions capable of achieving complete solubilization of perfume concentrates to
give an essentially clear liquid, especially for the purpose of preparing perfume
compositions.
 Another main object of the present invention is to solve the novel technical problem
consisting in the provision of a solution which makes it possible to effect the
abovementioned solubilization of perfume concentrates with the aid of solubilizers
which are neutral or substantially neutral towards the olfactory properties of said
perfume concentrate, especially with a view to preparing perfume compositions of
excellent quality.
 Another main object of the present invention is to solve both the novel technical
problems stated above by means of a solution which is free of ethanol or alcohol and
which does not use water, ethanol or mixtures thereof as co-solvent.
 The invention makes it possible for the first time to solve all these technical problems
in a satisfactory and simple manner which can be used on the industrial and cosmetic
scale, especially for the development of ethanol-free or alcohol-free perfume
compositions of excellent quality, particularly perfumes and toilet waters.
 Thus, according to a first feature, the present invention provides an ethanol-free or
alcohol-free composition comprising a hydrofluoro ether, characterized in that it
comprises at least one polyacid ester.
 It has been discovered, surprisingly, that the combination of a hydrofluoro ether and a
polyacid ester, acting as co-solvent, makes it possible to effect a virtually perfect or
perfect solubilization of perfume concentrates to afford an essentially clear solution
for the manufacture of perfume compositions of excellent quality. Moreover, it has
been observed, also surprisingly, that the combination of the hydrofluoro ether and the
polyacid ester forms a solubilizer which is neutral or essentially neutral from an
olfactory point of view towards the perfumes in question.
 The hydrofluoro ether component is preferably a perfluorinated component. These
compounds are well known to those skilled in the art; they are for example of the type
 described in the document WO 99/11225 and can have the general formula
CnHmFp—O—CxHyFz, in which n is a number ranging from 1 to 12, m is a number
ranging from 0 to 25, p is a number ranging from 0 to 11, m+p=2n+1, x is a number
from 1 to 12, y is a number from 0 to 25, x is a number from 0 to 11 and y+z=2x+1. In
this formula, m and y may not be equal to 0 simultaneously and p and z may not be
equal to 0 simultaneously, as described in said document to ensure the exactness of
the chemical formula.
 Some perfluorinated hydrofluoro ether compounds of the above general formula,
namely methoxynonafluorobutane, ethoxynonafluorobutane and
propoxyundecafluoropentane, are described in the document WO 99/26600. The
commercially available methoxyheptafluoropropane can also be used.
 The abovementioned polyacid ester is preferably an ester of a hydroxylated or non-
hydroxylated polyacid and is also preferably formed with a saturated or unsaturated,
linear or branched alcohol having between 1 and 30 carbon atoms, preferably between
1 and 12 carbon atoms, particularly ethanol, isopropanol or 2-ethylhexanol.
 The polyacid preferably has between 3 and 10 carbon atoms. The carbon chain of the
polyacid can be linear or branched and saturated or unsaturated with one or more units
of unsaturation.
 Furthermore, the carbon chain of the polyacids can be substituted by one or more
hydroxyl groups or can contain one or more ketone groups. The abovementioned
hydroxyl groups can be acetylated.
 The polyacid esters which can be used to carry out the invention are preferably
substantially non-polar.
 They can be partial or total esters of the polyacid.
 Preferably, all the acid groups of the polyacid are esterified.
 Preferably, where groups with long carbon chains are involved, these chains are
branched, as in the case of the 2-ethylhexyl group, which comprises 8 carbon atoms.
 The preferred ester groups are the ethyl, isopropyl and 2-ethylhexyl groups.
 The polyacids which can be used according to the invention are advantageously
selected from:
 →saturated diacids such as:
 malonic acid succinic acid glutaric acid adipic acid pimelic acid suberic acid azelaic
acid →monounsaturated diacids such as: fumaric acid maleic acid citraconic acid*
itaconic acid mesaconic acid *(branched diacid) →diunsaturated diacids such as:
muconic acid →monohydroxylated diacids such as: tartronic acid malic acid
citramalic acid →dihydroxylated diacids such as: dihydroxymaleic acid tartaric acid
→tetrahydroxylated diacids such as: dihydroxytartaric acid galactaric acid glucaric
acid →keto diacids such as: mesoxalic acid oxalacetic acid 2-oxoglutaric acid 3-
oxoglutaric acid →diketo diacids such as: 2,3-diketoadipic acid →saturated triacids
such as: tricarballylic acid citric acid (monohydroxylated triacid) →unsaturated
triacids such as: aconitic acid
 The preferred polyacids are citric acid and more particularly adipic acid.
 The citric acid esters are preferably triethyl citrate, tri(2-ethylhexyl) citrate and
acetyltriethyl citrate. These esters are commercially available.
 The preferred adipic acid esters are diisopropyl adipate (often called isoadipate) and
di(2-ethylhexyl) adipate. These esters are also commercially available.
 The proportions by weight of the polyacid ester relative to the hydrofluoro ether
component can vary within limits which do not substantially modify the olfactory
character of the perfumes. In general, the polyacid ester may represent from 0.1 to
30% by weight, particularly from 1 to 20% by weight, of the hydrofluoro ether
component.
 Provision can also be made for any other complementary component in said
composition, particularly a second co-solvent, such as a silicone, or a component for
improving the properties of a perfume composition, such as the persistence of said
composition on the skin, an example being a phthalate such as diethyl phthalate.
However, silicone is preferred because it simultaneously combines the property of a
co-solvent, or solubilizing additive, and the property of persistence.
 Preferably, the proportion of silicone will be calculated so as to correspond to about 1
to 20% by weight, based on the weight of the final perfume composition.
 Silicones which may be used are a dimethicone or a cyclomethicone, particularly the
commercially available pentacyclomethicone, or an organotrisiloxane such as the one
described in the PCT document published under the number WO 99/06018 and
marketed in particular under the name SILATRIPHENE by RHODIA, France.
Advantageously, it will be possible to use volatile silicones, particularly dimethicones
marketed by the American company DOW CORNING, such as DC200 Fluid 1
centiStokes or, preferably, DC200 Fluid 0.65 centiStokes.
 This composition can also comprise various additives normally used in the
preparation of perfume or toilet water compositions, for example UV filters,
antioxidants, antioxidants, colors, etc. Such complementary additives will generally
be added in a proportion which can range up to 2% by weight of the final
composition.
 In a first preferred embodiment, the invention provides an ethanol-free or alcohol-free
composition comprising a hydrofluoro ether, characterized in that it comprises the
following in percentages by weight: hydrofluoro ether . . . 65 to 85% citric acid
triester (such as triethyl citrate) . . . 4 to 7% 2nd co-solvent or solubilizer: silicone
such as DC200 Fluid from DOW CORNING, USA . . . 8 to 16% perfume concentrate
. . . 5 to 20%
 In a second preferred embodiment, the invention provides an ethanol-free or alcohol-
free composition comprising a hydrofluoro ether, characterized in that it comprises the
following in percentages by weight: hydrofluoro ether . . . 65 to 85% perfume
concentrate . . . 0.5 to 20% iso-adipate (or diisopropyl adipate) . . . 10 to 20%
 Within the framework of the invention, the hydrofluoro ether generally serves to make
 up the remainder of the composition, but the latter can optionally comprise the various
additives normally used in the preparation of the abovementioned perfume or toilet
water compositions.
 It has been observed, within the framework of the invention, that compositions using
iso-adipate as the 2nd co-solvent or solubilizing additive generally have a less greasy
feel than compositions using the association or combination of citrate and silicone.
 This represents an important technical advantage, unexpected for those skilled in the
art, because the feel of compositions based on iso-adipate is thus closer to that of the
conventional alcoholic perfume compositions such as toilet waters and perfumes.
 According to a second feature, the present invention also covers the use of a polyacid
ester, as defined above, in combination with a hydrofluoro ether as solubilizer for a
perfume concentrate, especially with a view to preparing perfume compositions such
as perfumes or toilet waters.
 According to a third feature, the present invention also covers an ethanol-free or
alcohol-free perfume composition comprising a perfume concentrate and a
hydrofluoro ether, characterized in that it also comprises at least one polyacid ester in
a sufficient amount to give said composition an essentially clear appearance.
 This perfume composition will advantageously comprise from about 65 to about 85%
by weight of hydrofluoro ether component, based on the final weight of the perfume
composition.
 According to another advantageous characteristic of this perfume composition, it will
comprise from about 1 to about 20% by weight, preferably from 3 to 20% by weight,
of abovementioned polyacid ester, based on the final weight of the perfume
composition.
 According to another advantageous characteristic of the perfume composition, it will
comprise from about 5 to about 20% by weight of perfume concentrate. In this
context, the concentration of perfume concentrate in the case of toilet water will
generally be in the order of 5% by weight, based on the final weight of the toilet
water. The concentration of perfume concentrate in the case of perfume will generally
be between 10 and 20% by weight of the final perfume composition.
 Thus the perfume composition will preferably consist of a toilet water or a perfume.
 Of course, whether applying to the second feature or the third feature, various
modified embodiments result from the first feature. Thus the hydrofluoro ether and
the polyacid ester are as defined within the framework of the first feature. The same
applies to any other complementary component which may be present and which has
been described within the framework of the first feature.
 Furthermore, within the framework of any one of the features of the invention, the
composition can advantageously contain up to 2% by weight, based on the final
composition, of any additive normally used in the preparation of perfume
compositions such as perfumes or toilet waters, examples being UV filters,
antioxidants, colors, etc.
 The process for the preparation of the composition is easy to understand for those
skilled in the art. The general procedure will be initially to add the polyacid ester to
the perfume concentrate and then to add any complementary compounds, particularly
a second co-solvent, such as a silicone, or a component for improving the properties
of the perfume composition, such as the persistence of the composition on the skin, an
example being a phthalate mentioned above, any other additives, particularly UV
filters, antioxidants or colors, and finally the hydrofluoro ether component, which will
preferably be added last and may also generally make up the remainder of the
formulation.
 The present invention will now be illustrated with the aid of Examples of ethanol-free
or alcohol-free perfume and toilet water compositions with a totally clear appearance
or the appearance of a perfect solution; said Examples are given simply by way of
illustration and cannot therefore limit the scope of the invention in any way. Unless
indicated otherwise, the percentages in the Examples are given by weight.
 EXAMPLE 1
 Of an Ethanol-Free or Alcohol-Free Perfume Composition According to the
Invention
 This perfume composition has the following formulation: ethoxynonafluorobutane . . .
68% triethyl citrate . . . 8% commercially available perfume concentrate . . . 20%
diethyl phthalate . . . 4%
 This composition is prepared in the following manner:
 The triethyl citrate is first added to the commercially available perfume concentrate
and the two are intimately mixed; this is followed by addition of the diethyl phthalate
and finally the ethoxynonafluorobutane.
 The perfume composition prepared in this way, without ethanol or alcohol, is found to
have a totally clear appearance or the appearance of a perfect solution, and the
olfactory properties of the perfume concentrate are found to be totally preserved.
 EXAMPLE 2
 Of an Ethanol-Free or Alcohol-Free Perfume Composition According to the
Invention
 This perfume composition has the following ingredients: methoxynonafluorobutane . .
. 71% trioctyl citrate . . . 6% silicone ref. DC200 Fluid 0.65 cs from DOW CORNING
8% commercially available perfume concentrate . . . 15%
 This composition is prepared in a similar manner to that of Example 1, the silicone
being added after the citrate.
 Again it is found that this composition has a totally clear appearance or the
appearance of a perfect solution and that the olfactory properties of the perfumes are
totally preserved.
 EXAMPLE 3
 Of an Ethanol-Free or Alcohol-Free Perfume Composition According to the
Invention
 This perfume composition has the following ingredients: methoxyheptafluoropropane
. . . 75% triethyl citrate . . . 6% 50:50 by weight mixture of diethyl phthalate and
silicone DC200 Fluid 1 cs from DOW CORNING . . . 9% commercially available
perfume concentrate . . . 10%
 The mixture is produced in a similar manner to Examples 1 and 2, again giving an
ethanol-free or alcohol-free perfume composition with a totally clear appearance or
the appearance of a perfect solution, the olfactory properties of the perfumes being
preserved.
 EXAMPLE 4
 Ethanol-Free or Alcohol-Free Toilet Water Composition According to the
Invention
 This toilet water composition has the following ingredients:
methoxynonafluorobutane . . . 82% triethyl citrate . . . 3% pentacyclomethicone . . .
10% commercially available perfume concentrate . . . 5%
 This composition is prepared by the same mixing procedure as that described in the
previous Examples.
 EXAMPLE 5
 Ethanol-Free or Alcohol-Free Perfume Composition According to the Invention
 This perfume composition has the following ingredients, again in percentages by
weight: commercially available perfume concentrate, approx . . . 10
ethoxynonafluorobutane, approx . . . 77 diisopropyl adipate, approx . . . 13
 This composition using diisopropyl adipate as an ester co-solvent generally has a less
greasy feel than compositions using an association of citrate and silicone, affording
the unexpected important technical advantage that the feel of this composition is
closer to that of the conventional alcoholic perfume compositions such as toilet
waters.
 Other modified embodiments of these Examples are well known to those skilled in the
art and can include e.g. the incorporation of various other additives normally used in
the preparation of perfume compositions such as perfumes or toilet waters, examples
being UV filters, antioxidants, colors, etc. Such complementary additives will
generally be added in a proportion which can range up to 2% by weight of the final
composition.
 Field of Invention
The invention relates to perfume compositions which are free of lower alcohols such as ethanol.
Background of the Invention
Lower alcohols, primarily ethanol, is the most interesting solvent of fragrance oil in
perfumes. Ethanol evaporates quickly into the atmosphere, cools the skin and conveys a very desirable
refreshing feeling on the human skin.
Regulations for environmental protection have recently become more stringent, also regarding volatile
organic compounds. For this reason, one of the aims of the cosmetic industry is to reduce the high
content of ethanol in perfumes or to replace it completely.
EP 0687460 B1 refers to low-alcohol perfume compositions comprising a lower glycol having up to
six carbon atoms and/or a lower alcohol having four to six carbon atoms and at least four carbon atoms in
its principal chain, and further comprising 40 - 75 per cent by weight of ethyl alcohol.
US 5,736,505 discloses a non-alcoholic fragrance comprising a hydrophobic perfume base, water, a non-
ionic surfactant and glycereth-7triacetate.
US 6,774,101 refers to an alcohol-free translucent perfuming composition with a surfactant of HLB > 10
being polyethylenglycol ethersand heavy paraffins. A preparation temperature of 75 - 95 °C is
disadvantageous for that composition.
US 2007/0178144 refers to cosmetic O/W emulsions comprising at least one non-ionic primary emulsifier,
at least one secondary emulsifier, one or more cosurfactants and usual cosmetic oils with the proviso that
the water phase content of the emulsion is at least 70 wt-%.
The object of the present invention is to provide perfume compositions without lower alcohols but higher
perfume oil contents in a long-lasting stable preparation and storable in a broad temperature range.
A further object is to provide a complete olfactory restitution of fragrance oil connected with a long-time
olfactory stability.
A further object is to provide perfume compositions with conveying a fresh feeling and without stickiness
on the skin.
Summary of the Invention
The perfume composition of the invention with reduced alcohol content comprises a transparent,
translucent or milky white emulsion with an oil phase and a water phase wherein
1. (a) the oil phase comprises 25 to 95 wt-% of an oil mixture of aromatic perfume oils and 5 to 75 wt-%
of a non-aromatic solvent, the percentages relating to the total weight of the oil phase, and the solvent
has a logP value of >5, and the solvent is selected from Isododecane, Isohexadecane, Isoeicosane,
isoparaffine fluids, C13-C30 alkanes, Hydrogenated Didecene, Hydrogenated Didodecene, Hydrogenated
Polydecene, Hydrogenated Polydodecene, Hydrogenated Tridodecene, Hydrogenated Polyisobutene,
mineral oils, and a mixture of two ore more thereof, or the solvent is a linear silicone of the
Dimethicone type, a cyclic silicone or a mixture thereof;
2. (b) the water phase comprises an emulsifier and a buffer system;
3. (c) the amount of the aromatic oils is in the range of 1 to 35 wt-%, related to the total weight of the
perfume composition;
4. (d) the amount of monovalent C2-C5 alcohols in the oil phase or in the water phase or in both phases is
in the range of 0 to 5 wt-% , related to the total weight of the perfume composition; and
5. (e) the water phase and the oil phase comprises further cosmetically acceptable ingredients.
The term "perfume composition" refers to a product of usual perfumes but also to other fragrances such
as Eau de Cologne, pre shaves, after shaves, face waters, tonics etc.
"Perfume oils" refers to known substances for modifying the smell/odour of a product or providing a
smell/odour to a person. Mixtures of natural essential oils or synthetic fragrances are possible.
The oil phase of the composition comprises perfume oils, essential oils or a mixture thereof. Essential oils
which are smelling substances derived by physical processes, preferred distillations, from plants or spices
are also subsumed in perfume oils.
Examples of perfume oils are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems
and leaves (geranium, patchouli, petitgrain), fruits (anis, coriander, cumin, juniper), fruit skins (bergamot,
citrus, orange), roots (macis, angelica, cardamom, iris, calmus) wood (pine, sandalwood, guaiac, cedar,
rose), herbs and grasses (tarragon, lemon grass, salvia, thyme), needles and branches (pine, fir), resins and
balms (galbanum, elemi, benzol, myrrh, olibanum, opoponax). Further, animal raw materials such as zibet
and castoreum. Typical synthetic fragrances are products from the ester
type, ether type, aldehyde type, ketone type, alcohol type and hydrocarbontype.
Useful perfume oils include galaxolide (50 % of Isopropyl Myristate), Ethylene Brassylate, Hebanolide,
Globanone, Musk Ketone, MuskXylol, Trimofix, Sandalore, Boisambrene, Nerolidol, Cedramber, Iso E
Super, Irisantheme, Damascone Alpha, Orange Bresil, Filial,Aldehyde Alpha Hexyl Cinnamic, Farnesol,
Bacdanol, Ebanol, Guaiac Wood Acetate, Cedrenyl Acetate, Hexyl Salicylate, Verdox, Cis-3Hexenyl
Salicylate, Linalyl Acetate, Benzyle Salicylate and mixtures thereof. Other perfume oils are also possible
according to Int. Cosmetic Ingredient Dictionary and Handbook, 12th ed. 2008, Vol. 3, p. 3193-3200
(edited by CTFA, Washington DC, USA).
To obtain a fragrance mixture with a combination of perfume oils it is preferred to complete the perfume
oils by some aromatic substances such as alcohols e.g. benzylic alcohol, cis-3-hexenol, phenyl ethyl
alcohol, anysil alcohol, isoamyl alcohol, 4 hexen-1-ol,phenoxyethanol; or other substances e.g. ethyl
vanilline, vanilline, heliotropine, helional, coumarin, ethyl maltol, ethyl acetate, ethyl acetoacetate, 2-
methyl pyrazine, linalool oxide; and also non-odour substances such as phenoxypropanediol, trimethyl-
1,3-pentanediol,chlorphenesin, ethylhexyl glycerin, caprylyl glycol, glyceryl caprylate; and mixtures thereof.
More generally it is preferred to complete with raw materials having a logP between 0.5 and 2.
The term "reduced alcohol content" means that the content of monovalent C2-C5 alcohols such
as ethanol is in the range of 0 - 5 wt-%, preferably 0 - 2 wt-% and most preferably 0 wt-%.
It is also possible to add to the oils such substances as Isononyl Isononanoate, Octyldocenol,
linear silicones of the Dimethicone type and cyclic silicones, Diethyl Hexyl Carbonate, Isopropyl
Myristate, Ethylhexyl Palmitate, PG, DPG, TPG, DPPG, Ethyl Phtalate, Ethyl Hexyl Stearate, Decyl
Cocoate, Dioctyl Carbonate, Cetearyl Ethyl Hexanoate, Decyl Oleate, Isocetyl Palmitate, Cetearyl
Isononanoate, Myristyl Myristate, Hexyl Laurate, Isopropyl Isononanoate, Isopropyl Palmitate, Isopropyl
Laurate, C12-15 Alkyl Benzoate, pentaerythritol esters(e.g. Pentaerythrityl Tetracaprylate/Tetracaprate
or Dipentaerythrityl Pentaisononanoate), but this is not preferred.
The solvents in the oil phase preferably have a calculated log P value in the range 5 to 12, more preferable
5 to 9, where P stands for the octanol/water partitioning coefficient of a material, i.e. the ratio between its
equilibrium concentration in octanol and water, which is a measure of hydrophobicity. High partitioning
coefficient values are more conveniently given in the form of their logarithm to the base 10, log P. While
log P values can be measured experimentally, and measured log P data is available for many perfumes,
log P values are most conveniently calculated. There are several recognised calculation or estimation
methods available commercially and/or described in the literature (see for example A. Leo, Chem. Rev.
93(4), 1281-1306, (1993), "Calculating log P oct from structures"). Generally these models correlate highly
but may for specific materials produce log P values which differ in absolute terms (by up to 0.5 log units
or even more). However, no one model is universally accepted as the most accurate across all compounds.
This is particularly true for estimates on materials of high log P (about 5 or greater). In the present
specification, calculated log P values are obtained using the estimation software of Syracuse Research
Corp., SRC, which is well-known to the scientific community, and accepted as providing high-quality
predictions of log P values. References to calculated log P values thus mean values obtained using the
a.m. software.
Most preferred solvents are Isohexadecane (logP 7.79), C15-C19 Alkane, C13-C16 Isoparaffin (logP 7.63),
and mixtures thereof. Other useful solvents are Isoeicosane (LogP 10.09), Isododecane (logP 6.16), paraffin
oil ISO W 05.
Preferably the oil phase comprises 40 to 70 wt-% of the aromatic oil or oil mixture and 20 to 45 wt-% of
the non-aromatic solvent, related to the total weight of the oil phase.
The amount of the aromatic oil is preferably in the range of 5 - 30 wt-%, especially 7 - 23 wt-%.
The emulsifier in the water phase is a non-ionic emulsifier or a mixture of non-ionic emulsifiers or
preferred a mixture of a non-ionic emulsifier with an emulsifier or a mixture of emulsifiers having one or
more acid functions.
Preferred non-ionic emulsifiers are selected from the group consisting of glyceryl partial esters,
polyglyceryl partial esters, sorbitanpartial esters, sorbitol partial esters, carbohydrate
esters, (alkylpoly)glycosides and mixtures thereof. The used carboxylic acids and alcohols, respectively, are
preferably C6-C22 carboxylic acids and C6-C22 alcohols, respectively. Examples are Polyglyceryl-2
Laurate,Polyglyceryl-3 laurate, Polyglyceryl-4 Laurate, Polyglyceryl-5 Laurate, Polyglyceryl-6
Laurate, Polyglyceryl-10 Laurate, Polyglyceryl-4Dilaurate, Polyglyceryl-4 Stearate, Polyglyceryl-
4 Isostearate, Polyglyceryl-4 Cocoate, Polyglyceryl-4 Oleate or Polyglyceryl-4 Caprate. Non-ionic
emulsifiers with ethoxylated branches can also be used.
Preferred anionic emulsifiers in mixture with nonionics are e.g. sulfates, sulfonates, citrates,
sulfosuccinates, succinates, tartrates and phosphates esterified with C6-C22 alcohols. Examples are dilauryl
citrate or disodium lauryl sulfosuccinate. The anionic emulsifier can be neutralised with e.g. Na or K.
Anionic emulsifiers with ethoxylated branches can also be used.
Special preferred emulsifiers are e.g. a mixture of polyglyceryl-4 laurate and dilauryl citrate (e.g. Tego®
Care PL4 of Degussa) anddilauryl citrate and disodium lauryl sulfosuccinate (e.g. Rewopol® SB F 12 P of
Degussa) or a mixture of Polyglyceryl-4 Laurate anddisodium lauryl sulfosuccinate or a mixture
of Polyglyceryl-3 Laurate (e.g. Hydramol® TGL Ester of Noveon) and Polyglyceryl-4 Laurateand Sorbitan
Laurate (e.g. Tego® SML of Degussa) and Disodium Lauryl Sulfosuccinate.
The range of the solvent is usually 0.1 to 20 wt-%, preferably 0.5 to 10 wt-%, more preferred 2 to 10 wt-%,
related to the total weight of the perfume composition.
The range of the emulsifier is usually 0.1 to 20 wt-%, preferably 0.5 to 12 wt-%, especially 0.5 to 2 wt-%. A
further preferred range of the emulsifier is 3 to 10 wt-%.
The buffer system in the water phase plays a very important role for the stability of the whole emulsion
composition.
By the buffer system the well-known pH drop which is described for aromatic substances due to, for
example, some ester hydrolysis (Linalyle acetate, benzyl acetate or allyl amyl glycolate) or
any aldehyde oxidation (Aldehyde α-hexyl cinnamic, helional or lilial).
The buffer system comprises at least one inorganic or organic component and preferably a mixture of
components, inorganic and/or organic.
Special buffer systems are sodium dihydrogenphosphate / disodium hydrogenphosphate, citric
acid/trisodium citrate, disodium citrate/HCl, potassium hydrogen phthalate/HCl, (potassium
hydrogen phthalate/HCl)/NaOH, (disodium citrate/ HCl)/NaOH, potassiumdihydrogen
 phosphate/disodium hydrogen phosphate, sodium barbital/HCl, borax solution/HCl ,
((glycine+NaCl)/HCl)/NaOH, citric acid/disodium hydrogen phosphate, sodium acetate/acetic
acid, imidazole/HCl, triethanol amine + titriplex III/HCl, tris(hydroxymethyl) aminomethane/HCl, sodium
carbonate/sodium hydrogen carbonate and mixtures thereof.
Specially preferred are sodium dihydrogenphosphate/disodium hydrogenphosphate as well as citric
acid/trisodium citrate.
Until now it has only been possible to formulate chemically stable aromatic perfume oils in water
emulsions. It was almost impossible to obtain a stable nanoemulsion containing more than 0.1 wt-% of
any buffer components. This refers to a one-month test in an oven at 45 °C, which is a usual stability test.
In this connection, the term "stable emulsion" means a particle size profile of the emulsion maintained for
at least two months at room temperature. Analyses were made with the Dynamic Light Scattering (DLS)
method, in which the coefficient of diffusion of the particles in solution was measured. Sample solutions
were diluted by factor 10 with de-ionised water. The measuring took place by dynamic light scattering
with a Malvern HPPS 3.1 at 25 °C for a duration of 100 seconds. The coefficient can be converted by the
Stokes-Einstein equation to a mean hydrodynamic radius of the emulsion droplets (equal to particles).
The particle size of the droplets of the present invention are in the range of 5 nm to 1 µm; this means the
oil droplets in the water phase or the water droplets in the oil phase. Preferred ranges are 5 to 200 nm,
especially 10 to 50 nm.
The perfume composition of the present invention can be a milky white emulsion, a translucent emulsion
or a transparent emulsion. The emulsion is preferably a translucent to transparent emulsion, more
preferred a transparent emulsion with a transmission of more than 90 % to 100 %. Transparent emulsions
have a particle diameter of 5 to 35 nm, translucent emulsions have a particle diameter of 35 to 95 nm.
The content of perfume oils and/or essential oils is in the range of 1 to 35 wt-%, preferably 5 - 20 wt-%,
more preferred 7 - 15 wt-% related to the total weight of the perfume composition.
The present invention provides a technique for preparing a low-viscosity, low skin-irritating, fine and
prolonged-stability emulsion containing a large amount of perfuming compound, as typically used for
impregnating fragrance emulsions, sprayable low alcohol or alcohol-free perfuming emulsions or lotions.
Further important improvements are:
1. (1) Without the presence of lower alcohols or with largely reduced alcohol contents, a significantly
better olfactory restitution of the fragrance's typical scent is possible, along with a longer lasting
effective stability as compared to e.g. common Eau de Toilettes.
2. (2) The special selection of the components of the inventive perfume composition does not require
high temperatures for the preparation of the emulsions, so that losses or partial losses of temperature-
sensitive perfume oils or essential oils are avoided.
3. (3) Perfume compositions with high loaded with high loads of fragrance parts in transparent or
translucent quality are possible.
4. (4) A long-term stability of the present invention's emulsions over the very broad temperature range
from -20°C to +45°C/55°C was established in the accelerated aging test.
5. (5) The emulsions of the invention have a very good feeling to the skin and greatly reduce the feeling
of stickyness due to the low content of surfactant.
6. (6) The emulsions are skin-friendly and provide only a very low irritation because of low surfactant
concentrations.
The inventive preparation also contains further cosmetic auxiliary and carrier substances as they are used
conventionally in such compositions, for example, water, floral waters, preservatives, colourings, chelating
agent such as EDTA and the like, polyols (such asglycerine, polyglycols, PEG-400, sorbitol), UVA and UVB
filters, gelling substances, tanning agents, polymers, copolymers, stabilisers and mixtures thereof, with the
proviso that only substances for maintaining a translucent or transparent composition be selected.
The composition according to the invention can also advantageously contain antioxidants, quencher
molecules and radical scavengers. Such substances include vitamins such as vitamin C and derivatives
thereof, for example, ascorbic acetate, ascorbic phosphate, andascorbic palmitate; vitamin A and
derivatives thereof; folic acid and derivatives thereof; vitamin E and derivatives thereof such asTocopheryl
Acetate, Tocopheryl Linoleate, Tocopheryl Phosphate; flavones or flavonoids; amino acids, such
as histidine, glycine, tyrosine,tryptophan, and derivatives thereof; carotenoids and carotenes such as α-
carotene, β-carotene and mixtures thereof, with the same proviso as above. Well-known antioxidants are
for example BHT, BHA, Tinogard® TT, Tinogard® TS, Tinogard® NOA (from Ciba), TBHQ, Propyl
Gallate, Vitamin E TPGS (Tocophersolan), Parsol Guard® (from DSM) and various mixtures none
under Covi-OX® (from Cognis) or Oxynex® (from MERCK); Quenchers as Tinoguard® Q (from Ciba),
Spectrasolv® (from The Hallstar Company) or Oxynex® ST (from Merck).
The use of the cosmetic preparations according to the invention can be realized in the form of e.g. Eau de
Toilettes, sun screen gels, after sun products, lotions, body gels, after shaves, pre shaves, Colognes,
moisturizing Eau de Toilette.
The manufacture of such products is carried out in a way known to a person skilled in the art.
Below, the invention will be described in detail by examples. If not specified otherwise, all percentages are
weight percentages.
The accompanying drawings show
Fig. 1
Exemplified graph with long-term stability of the emulsion according to Example 4 with intensity-
weighted size distribution against the particle radius (r)
Example 1 Perfume I
Phase A
Water 4.0
Polyglyceryl-4 Laurate 4.6
Isohexadecane 3.8
Fragrance mixture with perfume oils (6.5) (inter alia Iso E Super, Lilial) and aromatic alcohols (1.5) 8.0
(inter alia Benzyl Alcohol)
Glycerine 2.5
Disodium Lauryl Sulfosuccinate 0.5
Phase B
Water q.s. ad
100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The ingredients of phase A are mixed at about 50°C with 350-450 rpm to reach a homogenous mixture.
Phase B ingredients are mixed separately to dissolve the salts in the water. After that phase B is added
slowly to phase A over about 15 - 30 minutes with an increasing speed of 350 to 1000 rpm.
Homogenisation at 900 - 1000 rpm for 10 - 20 minutes is possible. Perfume I is a translucent
emulsion.Example 2 Perfume II
Phase A
Water 4.4
Polyglyceryl-4 Laurate 4.6
Isohexadecane 3.8
Fragrance mixture with perfume oils (6.0)1 and aromatic alcohols (1.5) 7.5
Glycerine 2.5
Disodium Lauryl Sulfosuccinate 0.5
Phase B
Water q.s. ad
100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
1
Mixture of Galaxolide®, Iso E Super®, Habanolide®, Hedione®, Orange EO from
Brazil, Dihydromyrcenol, Benzyle salicylate,Linalool, Linalyle acetate, Helional®, Alpha Damascone,
Ald. Alpha Hexyl cinnamic.
The procedure is according to Example 1. Perfume II is a translucent emulsion. Example 3 Perfume III
Phase A
Water 15.0
Polyglyceryl-4 Laurate 16.0
Isohexadecane 13.5
Fragrance mixture with perfume oils (24.5) (Perfect Match) and aromatic alcohols (5.5) (inter 30.0
alia Phenoxyethanol)
Glycerine 9.2
Disodium Lauryl Sulfosuccinate 1.5
Phase B
Water q.s. ad
100
Sodium Dihydrogenphosphate 0.15
Disodium Hydrogenphsophate 0.05
The procedure is according to Example 1. Perfume III is a transparent emulsion. Example 4 Perfume IV
Phase A
Water 4.0
Polyglyceryl-4 Laurate 4.5
Isohexadecane 3.8
Fragrance mixture with perfume oils (6.8) (Perfect Match) and aromatic alcohols (1.5) (inter 8.3
alia Benzyl Alcohol
Glycerine 2.5
Disodium Lauryl Sulfosuccinate 0.5
Phase B
Water q.s. ad
100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume IV is a translucent emulsion.
The graph of Fig. 1 shows that samples with different storage temperatures of 4°C, 20°C, 37°C, and 45°C
after eight weeks storage time have no alterations in the size distribution. This underlines the unique
long-term stability of the emulsion. Additionally, an increased olfactory restitution of the fragrance's
typical scent is to be noted. Example 5 Perfume V
Phase A
Water 4.0
Polyglyceryl-4 Laurate 4.6
C13-C16 Isoparaffins 4.0
Fragrance mixture with perfume oils (7.0) (Perfect Match) and aromatic alcohols (1.5) 8.5
Glycerine 2.5
Disodium Lauryl Sulfosuccinate 0.4
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume V is a translucent emulsion. Example 6 Perfume VI
Phase A
Water 6.0
Polyglyceryl-4 Laurate 4.5
Isohexadecane 3.8
Fragrance mixture with perfume oils (6.5) and aromatic alcohols (1.5) 8.0
Glycerine 3.0
Disodium Lauryl Sulfosuccinate 0.4
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.75
Disodium Hydrogenphsophate 0.25
Ethanol 5.0
The procedure is according to Example 1. Perfume VI is a translucent emulsion. Example 7 Perfume VII
Phase A
Water 4.0
Polyglyceryl-4 Laurate 4.8
Hydrogenated Polydecene 3.9
Fragrance mixture with perfume oils (6.5) and aromatic alcohols (1.5) 8.0
Glycerine 3.0
Disodium Lauryl Sulfosuccinate 0.4
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume VII is a translucent emulsion. Example 8 Perfume VIII
Phase A
Water 1.0
Polyglyceryl-4 Laurate 0.8
Isohexadecane 0.6
Fragrance mixture with perfume oils (1.0) and aromatic alcohols (0.3) (inter alia Benzyl Alcohol1.3
Glycerine 0.5
Disodium Lauryl Sulfosuccinate 0.1
Phase B
Water q.s. ad 100
Potassium Dihydrogenphosphate 1.0
Disodium Hydrogenphsophate 0.3
The procedure is according to Example 1. Perfume VIII is a translucent emulsion. Example 9 Perfume IX
Phase A
Water 3.5
Polyglyceryl-4 Laurate 4.8
Isohexadecane 4.0
Fragrance mixture with perfume oils (8.0) and aromatic alcohols (2.0) 10.0
Glycerine 2
Disodium Lauryl Sulfosuccinate 0.5
Phase B
Water q.s. ad 100
Citric Acid 0.1
Trisodium Citrate 0.9
The procedure is according to Example 1. Perfume IX is a translucent emulsion. Example 10 Perfume X
Phase A
Water 6.0
Polyglyceryl-4 Laurate 4.6
Isohexadecane 3.8
Fragrance mixture with perfume oils (7.0) and aromatic alcohols (1.5) 8.5
Glycerine 3.0
Disodium Lauryl Sulfosuccinate 0.4
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume X is a translucent emulsion. Example 11 Perfume XI
Phase A
Water 9.0
Polyglyceryl-4 Laurate 10.0
Isohexadecane 8.0
Fragrance mixture with perfume oils (15) and aromatic alcohols (3.5) (inter alia Benzyl Alcohol)18.5
Glycerine 5.0
Disodium Lauryl Sulfosuccinate 1.0
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.5
Disodium Hydrogenphsophate 0.1
The procedure is according to Example 1. Perfume XI is a translucent emulsion. Example 12 Perfume XII
Phase A
Water 7.0
Polyglyceryl-4 Laurate 8.0
Cyclohexasiloxane & Cyclopentasiloxane 6.5
Isopropyl Myristate 1.0
Fragrance mixture with perfume oils (11) and aromatic alcohols (3) (inter alia Phenoxyethanol14.0
Glycerine 4.5
Disodium Lauryl Sulfosuccinate 1.0
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.6
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume XII is transparent. Example 13 Perfume XIII
 Phase A
Water 4.0
Polyglyceryl-4 Laurate 4.5
Isohexadecane 3.8
Fragrance mixture with perfume oils (6) and aromatic alcohols mixed with Helional (1.5)7.5
Glycerine 3
Disodium Lauryl Sulfosuccinate 0.4
Phase B
Water q.s. ad 100
Sodium Dihydrogenphosphate 0.8
Disodium Hydrogenphsophate 0.2
The procedure is according to Example 1. Perfume XIII is milky white.