The present invention concerns a composition, preferably a stick composition, more
preferably a kajal stick composition (stick composition for the eyes), preferably of a
diameter of from 0.5 to 3 mm, comprising specific ingredients.
Eye make-up is of interest for women around the world. Among the different available
products, one can notably find mascaras, kohls and liners.
Particularly, when using liners, the goal is to apply the composition on the upper eyelid
and the waterline (i.e. just below the eyes); however, such a precise application is not
possible for most of the eyeliners, because they may cause eyes irritation.
Moreover, it is difficult to obtain liners which present good transfer properties of the
composition onto the skin.
Finally, there is a continuous need for obtaining an eye make-up with a certain thickness
15 of deposition and presenting good color intensity, with only one stroke and without
breaking the stick.
The invention proposes a make-up composition, preferably anhydrous and preferably in
the form of a stick, preferably a kajal stick, which is able to deliver the adequate make-up
20 in one stroke application. The texture of said composition is non-sticky and non-drying.
I The composition easily glides on the eye water line upon application, without discomfort,
l
andlor without worrying about irritation and/or watery eyes.
Preferably, the composition of the invention creates smudge-free bold lines on eyelids,
which preferably last for up to a few hours (i.e. 6-70h) and which are intense.
25 Finally, the composition of the invention is easy to manufacture, to pour and to mold. It is
stable for at least one month, preferably lwo months, at a temperature of up to 45°C.
Thus, the composition of the invention shows good stability, a good color intensity,
smoothness and good moldability upon preparation, notably for succeeding to obtain a
30 very thin slick having a diameter of less than 3 mm.
The present invention relates to a composition, preferably stick composition, more
preferably kajal stick composition, preferably of a diameter of from 0.5 to 3 mm,
comprising:
3 5 -waxes comprising :
at least one wax having a melting point lower than 75"C,
2
* at [east one wax having a melting point of at least 75°C and including at least
polyethylene wax and synthetic wax,
- at least one pigment chosen from carbon black and metallic oxides,
- at least one silicone volatile oil,
- at least one non-volatile oil, and
- at least one polymer chosen from liposoluble film-forming polymers, semi-crystalline
polymers and their mixtures.
Preferably, the composition is anhydrous. By "anhydrous", it is meant that the composition
comprises less than 3% by weight of the total weight of water, preferably less than 2%,
preferably less than I%pre,fe rably less than 0,5% by weight. Preferably, the composition
is devoid of water.
Without any mention of the contrary, the amounts are expressed by weight of the total
weight of the composition.
The invention also relates to a process for make-up of the eye, comprising applying the
composition of the invention around the eye, preferably on the eye water line.
Preferably, the composition comprises at least one of the following features:
- it comprises an amount of wax(es) having a melting point lower than 75°C of from 1 to
20% by weight, preferably of from 2 to 18% by weight, preferably of from 2.5% to 15% by
weight; preferably it comprises from 0.5% to 10%, preferably from 1% to 5% by weight of
candelilla wax, andlor from 1% to 15%, preferably from 5% to 10% by weight of waxes
obtained by hydrogenating esterified olive oil with stearyl alcohol;
- it comprises from 5 to 15% by weight of polyethylene wax, and from 3 to 10% by weight
of synthetic wax:
- it comprises from 5% to 25% by weight, preferably from 10% to 20% by weight of
pigments;
- it comprises from 10% to 60% by weight, preferably from 20% to 50% by weight, more
preferably from 25% to 40% by weight of volatile silicon oil;
- it comprises at least 10% by weight, preferably at least 15% by weight of non-volatile oil,
preferably from 10% to 35% by weight, preferably from 15% to 30% by weight of nonvolatile
oil;
- it comprises the polymer in a solids content ranging from 1% to 15% by weight, for
instance, from 2% to 10% by weight,
the percentages being by weight of the total weight of the composition.
Characterization of the stick
Advantageously, the composition according to the invention is a slick composition. The
5 hardness of the stick composition according to the invention can be such that the
composition is self-supporling and can disintegrate readily to form a satisfactory deposit
on the eyes.
Preferably it has a hardness varying from 220 to 260 g
The hardness is measured according to the following protocol:
10 The stick 1s stored at 20°C for 24 hours before the hardness measurement is taken.
The hardness can be measured at 20°C using the so-called "wire to cut the butter'"
method, which consists in transversally cutting a stick of the product, preferably cylindrical
revolution, using a rigid tungsten wire with a diameter of 250 pm by displacing the wire
relatively to the stick at a speed of 100 mmlmin.
15 The hardness of the samples of the compositions of the invention, expressed in Nm-', is
measured by means of a DFGS2 dynamometer sold by INDELCO-CHATILLON.
The measurement is reproduced three times and then averaged. The average of the three
values read using the dynamometer mentioned hereinabove, noted as Y, is given in
grams. This average may be converted into Newions then may be divided by L which
20 represents the highest dimension passed through by the wire. In the case of a cylindrical
stick, L is equal to the diameter (in meters).
The hardness can be converted into Nm-' by the equation herein below:
(Y x x 9.8)IL
For a measurement at a different temperature, the stock is stored 24 hours at this new
25 temperature before the measurement.
Wax hav~nqa rneltinq point lower than 75°C
The composit~ono f the invent~onc omprises at least one wax of which the melting point is
less than 75°C. Preferably, the composition according to the invention comprises at least
30 two different waxes having a melting point lower than 75°C.
The wax considered in the invention is in general a lipophilic compound, which is solid at
ambient 25°C having a reversible solidlliquid change of state, having a melting point in
particular greater than or equal to 30°C and less than 75°C.
4
The melting point of a solid fat can be measured using a differential scanning caiorimeter
(DSC), for example the calorimeter sold under the trade name "DSC 0100" by TA
Instruments with the "TA Universal Analysis" software.
According to the invention, the melting temperature corresponds more pa~icularlyto the
5 temperature of the most endothermic peak observed in BSC as described in the norm IS0
11357-3; 1999.
The measurement protocol can be as follows:
A sample of solid fat of about 5 mg is placed in a "sealed aluminum capsule" crucible.
When the solid fat is hard (wax), the sample is subjected to a first temperature rise from
10 20°C to 120°C, at a heating rate of 2°C I minute, and to 80°C, then left at isotherm of
100°C for 20 minutes, then is cooled from 120°C to 0°C at a cooling rate of 2°C I minute,
and finally subjected lo a second temperature rise from 0°C to 20°C at a heating rate of
2°C 1 minute.
The value of the melting temperature of the solid fat is the value of the top of the most
15 endothermic peak of the fusion cuwe observed, representing the variation in the
difference in power absorbed as a function of the temperature. In particular, the waxes of
the composition according to the invention, have a melting temperature greater than 30°C
and bener greater than 45°C.
20 More particularly, the wax having a melting point lower than 75°C is chosen from:
- the waxes obtained by catalytic hydrogenation of animal or plant oils that in particular
have C,C3, linear or branched fat chains, for example such as hydrogenated jojoba oil,
hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, as well as
the waxes obtained by hydrogenating esterified castor oil with cetyl alcohol, such as those
25 sold under the names Phytowax ricin 1 6 ~ 6a4nd~ 2 2~73"b y SOPHIM. Such waxes are
described in application FR-A-2792190. As waxes obtained by hydrogenating esterified
olive oil with stearyl alcohol (hydrogenated olive oil stearyl esters), mention can be made
of those sold under the name "PHYTOWAX Olive 7 8 L 57";
- waxes of animal or plant origin, such as beeswax, synthetic beeswax, candellila wax,
30 lanolin wax, berry wax, Japan wax, sumac wax, Orange and Lemon waxes, hydrogenated
Jojoba wax, in particular refined.
More preferably, the composition of the invention comprises at least one wax having a
melting point lower than 75°C chosen from candelilla wax, waxes obtained by
35 !iydrogenating esterified olive oil with stearyl alcohol (hydrogenated olive oil stearyl esters)
and their mixtures. More preferably, the composition of the invention comprises at least a
5
mixture of candelilla wax and waxes obtained by hydrogenating esterified olive oil with
stearyl alcohol.
Preferably, the composition of the invention comprises an amount of wax(es) having a
melting point lower than 75°C of from 1 to 20% by weight of the total weight of the
composition, preferably of from 2 to 18% by weight, preferably of from 2.5% to 25% by
weight.
More preferably, the composition of the invention comprises from 0.5% to 10%, preferably
from 1% to 5% by weight of candelilla wax, andlor from 1% to 15%, preferably from 5% to
10% by weight of the total weight of the composition of waxes obtained by hydrogenating
esterified olive oil with stearyl alcohol.
svnthetic wax
The composition of the invention also comprises at least one wax of which the melting
point is at least 75% and includes at least polyethylene wax and synthetic wax.
The polyethylene wax preferably has a melting point of at least 80°C, and preferably of
less than 100"C, preferably less than 95°C. Such a polyethylene wax may be sold under
the name Performalene 500-L Polyethylene by New Phase Technologies.
The synthetic wax according to the invention preferably has a melting point of at least
8O0C, and preferably of less than 10O0C, preferably less than 95°C. It is a non-polar wax,
preferably a polymethylene wax. Preferably it is a polymethylene wax comprising C25-
C60 unbranched hydrocarbons, with a molecular weight of 400-900 glmol, and a melting
point of around 81°C. Preferably the synthetic wax is Cirebelle 108 (which has a melting
point of around 81°C).
The composition may comprise polyethylene wax and synthetic wax, and futther other
waxes having a melting point of at least 75°C.
Such waxes may be chosen from microcrystailine wax padicularly of synthetic origin, such
as the ones commercialized under the name Tisco Wax 88, Cire HMP 88, Cire New
Mekon White USA, Be Square 1901195 Ambre, Paracera HW; and mixtures of
microcrystalline wax, synthetic wax and paraffin, such as Paracera 30540 from Paramelt.
6
Preferably, the composition of the invention comprises an amount of waxes having a
melting point of at least 75°C of from 5% to 30% by weight, preferably of from 40% to 25%
by weight of the total weight of the composition.
Preferably, the composition of the invention comprises from 5 to 15% by weight of the
5 total weight of the composition of polyethylene wax, and from 3 to 10% by weight of the
total weight of the composition of synthetic wax.
Piament
The composition of the invention comprises at least one pigment chosen from carbon
10 black and metallic oxides.
Preferably, the metallic oxides are iron oxides.
Preferably, the pigment is carbon black (61 77268:l). Carbon black may be from vegetal
or synthetic origin. More preferably, the pigment is carbon black from vegetal origin.
Other pigments may be present in the composition of the invention.
15 A pigment should be understood to mean inorganic or organic, white or colored particles.
Representative pigments that may be used in the practice of the invention include white,
colored, inorganic, organic, polymeric, nonpolymeric, coated and uncoated pigments.
Representative examples of mineral pigments include titanium dioxide, optionally surfacetreated,
zirconium oxide, zinc oxide, cerium oxide, iron oxides, chromium oxides,
20 manganese violet, ultramarine blue, chromium hydrate and ferric blue. Representative
examples of organic pigments include pigments of D & C type, and lakes based on
cochineal carmine, barium, strontium, calcium and aluminum. Pigments may also be
nacreous pigments, such as white nacreous pigments such as mica coated with titanium
or with bismuth oxychloride, colored nacreouspigmentssuch as titanium mica
25 with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an
organic pigment chosen from those mentioned above and nacreous pigments based on
bismuth oxychloride.
Preferably, they include titanium dioxide, D & C Red No. 7 Calcium Lake, D & C Red No.
21 Aluminum Lake, FD & C Yellow No. 5 Aluminum Lake, FD & C Blue no. 1 Aluminum
30 Lake, Blue 1 Lake and any other pigment or treated pigment known in the cosmetic arts.
The amount of pigment may vary depending on the application eiivisaged.
Preferably, the composition comprises from 5% to 25% by weight, preferably from 20% to
20% by weight of the total weight of the composition of pigments. Preferably, the
composition comprises from 10% to 20% by weight, preferably from 40% to 15% by
weight of the total weight of the composition of carbon black.
Volatile silicone oil
The composition of the invention comprises at least one volatile silicone oil
The term "volatile oil" refers lo an oil that has a non-zero vapor pressure, at ambient
temperature and atmospheric pressure, ranging in particular from 0.43 Pa to 40,000 Pa, in
particular ranging to 13,000 Pa, and more particularly ranging to 4,300 Pa.
The volatile silicone oil is preferably chosen from linear or cyclic silicone oils such as
linear or cyclic polydimethylsiloxanes (PDMS) having 3 to 7 silicon atoms.
By way of example of such oils, mention may be made of octyitrimethicone,
hexyltrimethicone, decamethylcyclopentasiloxane (cyclopentasiloxane or D5),
octamethylcyclotetrasiloxane (cyclotetradimethylsiloxane or D4), dodecamethylcyclohexasiloxane
(D6), decamethyltetrasiloxane (L4), polydimethysiloxanes such as those
sold under the reference DC 200 (1.5 cSt), DC 200 (5 cSt), DC 200 (3 cSt) by Dow
Corning, of KF 96 A of Shin Etsu; alone or in mixtures.
Preferably, the composition comprises at least 10% by weight of the total weight of the
composition, of volatile silicone oil, preferably at least 20% by weight, more preferably at
least 25 % by weight. Preferably, the composition comprises from 10% to 60% by weight
of the total weight of the composition, of volatile silicone oil, preferably from 20% to 50%
by weight, more preferably from 25% to 40% by weight.
Non-volatile oil
The composition oi the invention comprises at least one non-volatile oil,
"Non-volatile oil" refers to an oil of which the vapor pressure at 25°C and atmospheric
pressure, is not zero and less than 10-3 mm of Hg (0.13 Pa). By way of example, the
vapor pressure may be measured according to the static method or the method of effusion
by isothermic thermogravimetry, according to vapor pressure (norm OECD 104.).
The non-volatile oil may be polar or apolar (non-polar).
The non-volatile oil may be a hydrocarbon oil or a silicone oil. Preferably, it is a
hydrocarbon oil.
Non-polar non-volatile hydrocarbon oils are more particularly chosen from compounds
that comprise only carbon and hydrogen atoms.
Said oils, linear or branched, can be of mineral or synthetic origin such as for example:
- paraffin oil or derivatives thereof,
- squalane,
- isoeicosane,
I - naphthalene oil,
- polybutenes, hydrogenated or not, such as for example INDOPOL H-100,
10 INDOPOL H-300, INDOPOL H-1500 sold or manufactured by AMOCO,
- polyisobutenes, hydrogenated polyisobutenes such as for example Parleame
sold by NIPPON OIL FATS, PANALANE H-300 E sold by AMOCO, VlSEAL 20000 sold by
SYNTEAL, REWOPAL PIB 1000 sold by WITCO, or PARLEAM LlTE sold by NOF
Corporation,
15 - decenelbutene copolymers, polybutenelpolyisobuiene copolymers particularly
Indopol L-14,
- polydecenes and hydrogenated polydecenes such as for example PURESYN
10, PURESYN 150 or PURESYN 6 sold by EXXONMOBlL CHEMICAL),
- and mixtures thereof.
20
.i
I The composition can comprise at least one polar non-volatile hydrocarbon-based oil, in
J
particular chosen from:
- C10-C2aGlc ohols, preferably monoalcohols;
25 More particularly~, th-e C,,-C,, alcohols are saturated or not, branched or not, and comprise
from 10 to 26 carbon atoms.
Preferably, the C10-C26a lcohols are fat?\. alcohols, preferably branched when they contain
at least 16 carbon atoms.
As examples of fatty alcohols that can be used according to the invention, mention can be
30 made of linear or branched fatty alcohols, or natural such as for example alcohols coming
from plant substances (coconut, palm, etc.) or animal substances (tallow, etc.).
Of course, other long-chain alcohols can also be used, such as for example ether-alcohols
or so-called Guerbet alcohols.
Finally, ceriain more or less long cuts of alcohols of natural origin, such as for example
35 coco (Cq2t o CTGo)r tallow (CqGto C6) or compounds of the diol or cholesterol type, can
also be used.
9
Preferably a fatty alcohol comprising from 10 to 24 carbon atoms, and more preferably
from 42 to 22 carbon atoms is used.
As particular examples of fatty alcohols that can be used preferably, mention can be made
in particular of lauric, isosteayl, oleic alcohol, 2-butyloctanol, 2-undecyl pentadecanol, 2-
hexyldecylic alcohol, isocetylic alcohol, octyldodecanol and mixtures thereof.
According to one advantageous embodiment of the invention, the alcohol is chosen from
octyldodecanol.
- monoesters, diesters, triesters, optionally hydroxylated, of a C2-C8 mono or
polycarboxylic acid and a 6 2 - 6 8 alcohol.
In parlicular:
* monoesters of a 62-65 carboxylic and of a 6,-C8 alcohol, optionally
hydroxylated,
* the diesters of a 6 2 - 6 8 carboxylic diacid and of a C2-C8 alcohol, optionally
hydroxylated; such as diisopropyl adipate, diethyl-2 hexyl adipate, dibutyl adipate, or
diisosteaiyl adipate, 2-diethyl-hexyl succinate,
* the triesters of a C2-6, carboxylic triacide and of a C2-C8 alcohol, optionally
hydroxylated, such as the esters of citric acid, such as trioctyl citrate, triethylcitrate,
acetyltributyl citrate, tributyl citrate, acetyltributyl citrate.
- The esters of a C,-C8 polyol and of one or several C2-C8 carboxylic acids,
such as the diesters of glycol and of monoacids, such as neopentylglycol diheptanoate, or
the triesters of glycol and of monoacids such as triacetine.
-the ester oils, in particular having between 17 and 70 carbon atoms.
As examples. mention can be made of mono-, di- or tri- esters.
Ester oils can be hydroxylated or not.
The non-volatile ester oil can be chosen for example from:
" monoesters comprising between 17 and 40 carbon atoms in total, in
particular monoesters, having formula R,COOR2 wherein R1 is the remainder of a linear or
branched or aromatic fatty acid comprising from 4 to 40 carbon atoms, saturated or not,
and R2 is a hydrocarbon chain in particular branched containing from 3 to 40 carbon
atoms with the condition that R, + R2 is 17, as for example Purcellin oil (cetostearyl
octanoate), isononyl isononanoate, C,2 to 6 , s alcohol benzoate, 2-ethyl hexyi palmitate,
octyldodecyl neopentanoate, octyl-2-dodecyl stearate, octyl-2-dodecyl eiucale, isosteayl
isostearate, octyl-2 dodecyl benzoate, octanoates, decanoates or ricinoleates of alcohois
I0
or of polyalcohols, isopropyl myristate, isopropyl palmitale, butyl stearale, hexyl laurate, 2-
ethylhexyl palmitale, 2-hexyl decyl laurate, 2-octyldodecyl palmitate, 2-octyldodecyl
myristate.
Preferably, these are esters having formula RlCOOR2 wherein R, is the remainder of a
linear or branched fatty acid comprising from 4 to 40 carbon atoms and R, is a
hydrocarbon chain in particular branched containing from 3 to 40 carbon atoms, with R,
and R, being such that R1 + R, is 17.
More particularly, the ester comprises between 17 and 40 carbon atoms in total.
As preferred monoesters, mention can be made of isononyl isononanoate, oleyl erucate
andlor octyl-2-docecyl neopentanoaie;
* fatty acid monoesters, in particular from 18 to 22 carbon atoms, and in
particular lanolic acid, oleic acid, lauric acid, stearic acid, and diols, such as propylene
glycol monoisostearate.
* diesters, in particular comprising between 18 and 60 carbon atoms in total, in
particular between 18 and 50 carbon atoms in total. In particular diesters of carboxylic
diacid and of monoalcohols can be used, such as preferably diisostearyl malate, or the
diesters of glycol and of monocarboxylic acids, such as neopentylglycol diheptanoate,
propylene glycol dioctanoate, diethylene glycol diisononanoate, or polyglyceryl-2
diisosiearate (in particular such as the compound sold under the commercial reference
DERMOL DGDlS by Alzo);
* hydroxylated monoesters and diesters, preferably having a total number of
carbon ranging from 18 to 70, such as polyglyceryl-3 diisostearate, isostearyl lactate,
octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, glyceryl stearate;
* triesters, in particular comprising between 35 and 70 carbon atoms in total, in
particular such as triesters of carboxylic triacide, such as triisostearyl citrate, or tridecyl
trimellitate, or triesters of glycol and of monocarboxylic acids such as polyglyceryl-2
triisostearate;
* tetraesters, in particular having a total number of carbon ranging from 35 to
70, such as tetraesters of penthaeryihritol or of polyglycerol and of a monocarboxylic acid,
for example such as pentaerythrityl tetrapelargonate, pentaeryihrityl tetraisostearate,
pentaeryihrityl tetraisononanoate, glyceryl tri decyl-2 tetradecanoate, polyglyceryl-2
tetraisostearate or pentaerythrityl tetra decyl-2 tetradecanoate;
* polyesters obtained by condensing unsaturated fatty acid dimers andlor
trimers and diol such as those described in the patent application FR 0 853 634, such as
in particular dilinoleic acid and 1,4- bulanediol. Mention may parlicularly be made in this
respect of the polymer sold by Biosynthesis under the name Viscopiast 14436H (INCI
11
name: dilinoleic acidibutanediol copolymer), or polyol and diacid dimer copolymers, and
esters thereof, such as Hailuscent ISDA;
* dimer diol and mono- and dicarboxylic esters and polyesters, such as dimer
diol and fatty acid esters and dimer diol esters carboxylic diacid dimers, in particular that
5 can be obtained from a carboxylic diacid dimer particularly derived from the dimerization
of an unsaturated fatty acid, particularly C8 to C34, particularly 612 to Cz2, in particular CT6
lo CzO, and more particularly C,,, such as dilinoleic diacid esters and dilinoleic diol dimers,
for example such as those sold by NlPPON FINE CHEMICAL under the trade name
I LUSPLAN DD-DA~@an d DD-DM@;
10 * polyesters resulting from the esterification of at least one triglyceride of
carboxylic acid(s) hydroxylated by an aliphatic monocarboxylic acid and by an aliphatic
dicarboxylic acid, possibly unsaturated such as castor oil of succinic acid and of isostearic
acid sold under the reference Zenigloss by Zenitech;
* plant-based hydrocarbon-based oils such as fatty acid liquid triglycerides
15 (liquid at ambient temperature), in particular fatty acids having from 7 to 40 carbon atoms,
such as heptanoic or octanoic acid triglycerides or jojoba oil, in particular, mention can be
made of saturated triglycerides such as capryliclcapric triglyceride and mixtures thereof,
for example such as the one sold under the reference Myritol 318 from Cognis, glycerol
triheptanoate, glycerin trioctanoate, triglycerides of acid in C18~3s6u ch as those sold under
20 the reference DUB TGI 24 sold by Stearineries Dubois), and unsaturated triglycerides
such as castor oil, olive oil, ximenia oil, pracaxi oil.
j
- vinylpyrrolidonell-hexadecene copolymers, such as for example the one
sold under the name ANTAROIV V-216 (also called Ganex V216) by ISP (MW=7,300
25 gimol).
- dialkyl carbonates, the 2 alkyl chains possibly being identical or different,
such as the dicaprylyl carbonate sold under the name Cetiol CC@, by Cognis.
30 - and mixtures thereof.
Preferably, the non-polar non-volatile hydrocarbon oil is chosen from polybutenes,
hydrogenated or not.
Preferably, the polar non-volatile hydrocarbon-based oil is chosen from fatty alcohols
35 comprising from 20 to 24 carbon atoms, and more preferably from 12 lo 22 carbon atoms;
monoesters comprising between 17 and 40 carbon atoms in total, in particular monoesters
12
having formula R,COORZ wherein R, is the remainder of a linear or branched or aromatic
faMy acid comprising from 4 to 40 carbon atoms, saturated or not, and R2 is a hydrocarbon
chain in paiticular branched containing from 3 to 40 carbon atoms with the condition that
R, + R2 is 17; and mixtures thereof.
5 More preferably, the composition of the invention comprises a mixture of polar non-volatile
hydrocarbon-based oils, preferably of isononyl isononanoate and octyldodecanol.
Preferably, the non-volatile oil is chosen from polybutene, octyldodecanol, isononyl
isononanoate and their mixtures.
10
Preferably, the composition comprises at least 10% by weight, preferably at least 15% by
weight of non-volatile oil. Preferably, the composition comprises from 10% to 35% by
weight, preferably from 15% to 30% by weight of non-volatile oil.
15
The composition of the invention comprises at least one polymer chosen from liposoluble
film-forming polymers, semi-crystalline polymers and their mixtures.
As disclosed herein, the term "film-forming polymer" means a polymer capable, by itself or
*
20 in the presence of an auxiliary film-forming agent, of forming a continuous film that
adheres to a support, such as keratin materials.
Film-forming polymers include liposoluble polymers comprising less than 30% by weight
of a crystallizable portion as disclosed herein, or for example, comprising no crystallizable
portion at all.
25 Among the film-forming polymers that may be used in the compositions of the present
disclosure, non-limiting mention may be made of synthetic polymers, of free-radical type
or of polycondensate type, and polymers of natural origin, and mixtures thereof.
Non-limiting examples of liposoluble polymers that may be used as disclosed herein
30 include copolymers of vinyl esters wherein the vinyl group is directly linked to the oxygen
atom of the ester group and vinyl esters comprising a saturated, linear or branched
hydrocarbon-based radical of 1 to 24 carbon atoms, linked to the carbonyl of the ester
group, and of at least one other monomer, which may be chosen from vinyl esters
different from the vinyl ester already present, alkyl vinyl ethers the alkyl group of which
35 comprises from 2 to 24 carbon atoms, and allylic and methaliylic esters comprising a
saturated, linear or branched hydrocarbon-based rzdical of I to 24 carbon atoms, linked
13
lo the carbonyl of the ester group. These copolymers may be crosslinked using
crosslinking agents that may be of the vinylic type, of the allylic and methallylic type, such
as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and
divinyl octadecanedioate. Examples of such copolymers include the following copolymers:
vinyl acetate I allyl stearate, vinyl acetate I vinyl laurate, vinyl acetate I vinyl stearate, vinyl
acetate I octadecyl, vinyl propionate I laurate allyl, vinyl propionate ! vinyl laurate, vinyl
stearate I l-octadecene, vinyl stearate ! ethyl vinyl ether, vinyl propionate I cetyl vinyl
ether, vinyl stearate I allyl acetate, dimethyl-2, 2 octanoate vinyl I vinyl laurate, dimethyl-2,
2 pentanoate allyl I vinyl laurate, vinyl dimethylpropionate l vinyl stearate, allyl dimethyl
propionate ! vinyl stearate, vinyl propionate I vinyl stearate, crosslinked with 0 , 2%
divinylbenzene, vinyl dimethylpropionate I vinyl laurate, crosslinked with 0.2%
divinylbenzene, vinyl acetate l octadecyl vinyl ether, crosslinked with 0.2% of
tetraallyloxyethane, vinyl acetate 1 stearate allyl, crosslinked with 0.2% divinylbenzene,
vinyl acetate I l-octadecene, crosslinked with 0.2% divinylbenzene, and allyl propionate I
allyl stearate, crosslinked with 0.2% divinylbenzene.
Further non-limiting examples of these copolymers that may be used as disclosed herein
include the copolymers: vinyl acetatelvinyl laurate, vinyl propionatelallyl laurate, vinyl
propionatelvinyl laurate, and allyl 2,2-dimethylpentanoatelvinyl laurate.
Among additional liposoluble film-forming polymers that may also be used as disclosed
herein, non-limiting mention may be made of liposoluble homopolymers, for instance,
those resulting from the homopolymerization of vinyl esters comprising from 9 to 22
carbon atoms or oi alkyl acrylates or methacrylates, the alkyl radicals comprising from 2 to
24 carbon atoms.
Still additional non-limiting examples of liposoluble homopolymers that may be used
include those chosen from homopolymers of vinyl ester having C8-1230 alkyl groups, such
as polyvinyl laurate (in particular sold under the reference Mexomere PP by Chimex), and
polylauryl(meth)acrylates, these poly(meth)acrylates possibly being crosslinked using
ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate.
The liposoluble homopolymers and copolymers defined above are known and described,
for example, in French Patent Application FR-A-2,232,303; they may have a weightaverage
molecular weight ranging from 2,000 to 500,000, for instance, from 4000 to
200,000.
14
Among liposoluble film-forming polymers that may be used as disclosed herein, nonlimiting
mention may also be made of polyalkylenes, for example C2to Czoalkene
copolymers, for instance polybutene, alkylceiluloses with a linear or branched, saturated
or unsaturated Cl to C8 alkyl radical, for instance ethylceliulose and propylcellulose,
5 vinylpyrrolidone (VP) copolymers, such as copolymers of vinylpyrrolidone and of a C2to
Ce0, for example, C3to CzO, alkene. As examples of VP copolymers that may be used in
the invention, non-limiting mention may be made of VPlvinyl acetate, VPIethyl
methacrylate, butylated polyvinylpyrrolidone (PVP), VPIethyl methacylatelmethacylic
acid, VPleicosene, VPlhexadecene, VPltriacontene, VPlstyrene and VPlacylic acidllauyl
10 methacylate copolymers.
Preferably, the polymer is chosen from allyl stearate copolymers such as vinyl acetate 1
allyl stearate copolymers, polyvinyl laurate and their mixtures.
15 The at least one film-forming polymer may be present in the composition as disclosed
herein in a solids content ranging from 1% to 15% by weight, for instance, from 2% to
10% by weight relative to the total weight of the composition.
Volatile hvdrocarbon oil
20 The composition of the invention preferably further comprises at leasi one volatile
hydrocarbon oil.
The volatile hydrocarbon oil is preferably chosen from volatile hydrocarbon oils that have
from 8 to 16 carbon atoms and mixtures thereof, and in pafiicular:
25 - CB-C,, branched ~lkaness uch as iso-alkanes (also called isoparaffins) in
C,-C,,, isododecane, isodecane, isohexadecane, and for example the oils sold under the
trade names lsopars or Permetyls,
- linear alkanes, for, example such as ndodecane (612) and n-ietradecane
(C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL
30 14-97, as well as m~xtures thereof, the undecane-tridecane mixture (Cetiol UT), the
mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in examples 1 and 2 of
application W020081155059 of Cognis, and
- mixtures thereof.
15
Preferably, the composition comprises less than 15% by weight of volatile hydrocarbon oil.
Preferably, the composition comprisesfrom 1 to 10% by weight of volatile hydrocarbon oil,
preferably from 5% lo 10% by weight.
5
The composition according to the invention may also comprise any usual cosmetic
ingredient, which may be chosen especially from antioxidants, fragrances, preservatives,
neutralizing agents, surfactants, vitamins, moisturizing agents, emollients, hydrophilic or
lipophilic active agents and mixtures thereof.
10
Needless to say, a person skilled in the art will take care to select the optional additional
ingredients andlor the amounts thereof such that the advantageous properties of the
composition according to the inveniion are not, or are not substantially, adversely affected
by the envisioned addition.
15
Preferably, the composition according to the invention is a stick composition, preferably a
kajal stick composition. Preferably, the composition is in the form of a stick with a bullet
diameter comprised between 0.5 to 20 mm, preferably between 2 and 3 mm.
20 The invention also relates to a process for make-up of the eye, comprising applying the
composition of the invention around the eye, preferably on the eye water line.
The invention is illustrated in greater detail by the examples described below, which are
given as non-limiting illustrations.
25
Examples
The following formulations A to C of the invention, and comparative formula D, were
MICROCRYSTALLINE WAX (620-660)
ISONONYL ISONONANOATE
HYDROGENATED OLiVE OIL STEARYL ESTERS
Formula B is comparative because it does not comprise any synthetic wax.
(Polymethylene wax ; melting point = 80°C)
(Cirebelle 108)
CYCLOPENTASILOXANE
(CM5 L from Bluestar)
ISODODECANE
The pigments were mixed with isododecane, to obtain a pigmentary paste.
5 All other ingredients were heated at a temperature of around 105"C, and the pigmentary
paste was added to the molten mixture while stirring, until obtaining a homogenized
mixture.
The resulting mixture was poured into stick molds and molded.
1.5
8
7
10
formulas
6
30
Qsp
100
The formulations A to D of example 1 (i.e. formulations A to C of the invention, and
comparative formula D), were tested for their moldability and bullet formation. The results
15 are in the table below:
'1.5
9
8
6
27
Qsp
100
I I Easv to mold and I I
1.5
8
7
Formula / A / B J C
I Moldability buliet formation I Very thick and difficult to mold I
1.5
8
7
6
30
Qsp100
B
The results clearly show that the formuias of the invent~on are easy to mold and form
20 bullet, whereas the comparative formula does not form any lead and is thick and difficult to
pod in molds.

CLAIMS
1. Composition, preferably stick composition, more preferably kajal stick composition,
preferably of a diameter of from 0.5 to 3 mm, comprising:
5 - waxes comprising :
* at least one wax having a melting point lower than 75°C ,
* at least one wax having a melting point of at least 75°C and including at least
polyethylene wax and synthetic wax,
- at least one pigment chosen from carbon black and metallic oxides,
10 - at least one volatile silicone oil,
- at least one non-volatile oil, and
- at least one polymer chosen from liposoluble film-forming polymers, semi-crystalline
polymers and their mixtures.
15 2. Composition according to claim 1, wherein the wax having a melting point lower than
75°C is chosen at least from candelilla wax, waxes obtained by hydrogenating esterified
olive oil with stearyl alcohol and their mixtures.
3. Composition according to claim I or 2, wherein the synthetic wax is a polymethylene
20 wax, preferably a polymethylene wax comprising C25-660 unbranched hydrocarbons,
with a molecular weight of 400-900 glmol, and a melting point of around 81°C.
4. Composition according to any one of claims 1 to 3, wherein the metallic oxides are iron
oxides.
25
5. Composi!ion according to any one of claims 1 to 4, wherein the pigment is carbon
black, more preferably carbon black from vegetal origin.
6. Composition according to any one of claims 1 to 5, wherein the volatile silicone oil is
30 chosen from linear or cyclic silicone oils such as linear or cyclic polydimethylsiloxanes
(PDMS) having 3 to 7 silicon atoms, preferably from octyltrimethicone, hexyltrimethicone,
decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethyicyclohexasiloxane,
decamethyltetrasiloxane and polydimethysiloxanes.
7. Composition according to any one of claims 1 to 5, wherein the composition comprises
at least 10% by weight of the total weight of the composition, of volatile silicone oil,
preferably at least 20% by weight, more preferably at least 25 % by weight.
8. Composition according to any one of claims 1 to 7, wherein the non-volatile oil
comprises a non-polar non-volatile hydrocarbon oil of mineral or synthetic origin such as:
- paraffin oil or derivatives thereof,
- squalane,
- isoeicosane,
- naphthalene oil,
- polybutenes, hydrogenated or not,
- polyisobutenes, hydrogenated polyisobutenes,
- decenelbutene copolymers, polybutenelpolyisobutene copolymers,
- polydecenes and hydrogenated polydecenes,
- and mixtures thereof.
9. Composition according to any one of claims 1 to 8, wherein the non-volatile oil
comprises a polar non-volatile hydrocarbon-based oil, chosen from:
- CqO-Cz6 alcohols, preferably monoalcohols, preferably fatty alcohols
comprising from 10 to 24 carbon atoms, and more preferably from 12 to 22 carbon atoms;
- monoesters, diesters, triesters, optionally hydroxylated, of a C2-6, mono or
polycarboxylic acid and a C2-C, alcohol;
- the esters of a 6,-C, polyol and of one or several C2-C, carboxyiic acids,
such as the diesters of glycol and of monoacids, such as neopentylglycol diheptanoate, or
the triesters of glycol and of monoacids such as triacetine;
- the ester oils, in part~cular having between 17 and 70 carbon atoms,
preferably monoesters comprising between 17 and 40 carbon atoms in total, in patticular
monoesters having formula RqCOOR2 wherein R, is the remainder of a linear or branched
or aromatic fatty acid comprising from 4 to 40 carbon atoms, saturated or not, and R2 is a
hydrocarbon chain in pariicular branched containing from 3 to 40 carbon atoms with the
condition that R, + R2 is 17;
- vinylpyrrolidonell-hexadecene copolymers;
- dialkyl carbonates, the 2 alkyl chains possibly being identical or different,
such as the dicaprylyl carbonate;
- and mixtures thereof.
19
10. Composition according to any one of claims 1 to 9, wherein the non-volatile oil is
chosen from polybutene, octMdodecanoi, isononyl isononanoale and their mixtures.
11. Composition according lo any one of claims 1 to '10, wherein the polymer is chosen
5 from allyl stearate copolymers such as vinyl acetate I aliyl stearate copolymers, polyvinyl
laurate and their mi*ures.
12. Composition according to any one of claims 1 to 11, wherein it is anhydrous.
10 13. Composition according to any one of claims 1 to 42, which is in the form of a stick with
a bullet diameter comprised between 2 and 3 mm.
14. Composition according to any one of claims 1 to 13, wherein it comprises at least one
of the following features:
15 - it comprises an amountof wax(es) having a melting point lower than 75°C of from 1 to
20% by weight, preferably of from 2 to 18% by weight, preferably of from 2.5% to 15% by
weight; preferably it comprises from 0.5% to 10%, preferably from 1% to 5% by weight of
candelilla wax, andlor from 1% to 15%, preferably from 5% to 10% by weight of waxes
obtained by hydrogenating esterified olive oil with stearyl alcohol;
20 - it comprises from 5 to 75% by weight of polyethylene wax, and from 3 to 20% by weight
of synthetic wax;
- it comprises from 5% to 25% by weight, preferably from 10% to 20% by weight of
pigments;
- it comprises from 10% to 60% by weight, preferably from 20% to 56% by weight, more
25 preferably from 25% to 40% by weight of volatile silicon oil;
- if comprises at least 10% by weight, preferably at least 15% by weight of non-volatile oil,
preferably froni 10%; to 35% by weight, preferably from 15% to 30% by weight of nonvolatile
oil;
- it co~nprises the polymer in a solids conlert ranging from 1% to 15% by weigh-(, for
3 0 instance, from 2% lo 20% by weight,
the percentages being by wight i:f the tolzl weight of the composition.
15. Process for make-up of the eye, comprising app!ying the composition of any one of
claims 1 to 14 around the eye, preferably on the eye vder line.