U.S. patent application number 11/491077 was filed with the patent office on 2007-08-23 for process for coating eyelashes.
Invention is credited to Nathalie Jager Lezer, Florence Lahousse.
Application Number | 20070196306 11/491077 |
Document ID | / |
Family ID | 36157704 |
Filed Date | 2007-08-23 |
United States Patent
Application |
20070196306 |
Kind Code |
A1 |
Jager Lezer; Nathalie ; et
al. |
August 23, 2007 |
Process for coating eyelashes
Abstract
The disclosure relates to a process for coating keratin fibers,
comprising the application to the keratin fibers of at least one
coat of at least one dry-applicable composition presented in the
form of a stick. The disclosure also relates to a process for
coating keratin fibers, comprising placing the fibers in contact
with at least part of the surface of a stick of a dry-applicable
composition, and causing a relative displacement between the
surface of the stick and the fibers so as to bring about erosion of
the composition and its application to the fibers in the form of a
deposit of at least one coat.
Inventors: |
Jager Lezer; Nathalie;
(Verrieres-le-Buisson, FR) ; Lahousse; Florence;
(Thiais, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
36157704 |
Appl. No.: |
11/491077 |
Filed: |
July 24, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60704423 |
Aug 2, 2005 |
|
|
|
Current U.S.
Class: |
424/70.7 ;
424/70.12 |
Current CPC
Class: |
A61Q 1/10 20130101; A61K
8/90 20130101; A61K 8/0229 20130101; A61K 8/897 20130101; A61K
8/8111 20130101; A61K 8/927 20130101; A61K 8/585 20130101 |
Class at
Publication: |
424/070.7 ;
424/070.12 |
International
Class: |
A61K 8/89 20060101
A61K008/89 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 22, 2005 |
FR |
05 52287 |
Claims
1. A process for coating keratin fibers, comprising: applying to
the keratin fibers at least one coat of at least one composition in
the form of a stick, wherein the composition is dry-applicable.
2. The process according to claim 1, wherein the stick has a
hardness ranging from 500 to 18,200 Pa.
3. The process according to claim 2, wherein the composition has a
hardness ranging from 900 to 10,000 Pa.
4. The process according to claim 3, wherein the composition has a
hardness ranging from 1800 to 8200 Pa.
5. The process according to claim 1, wherein the composition
comprises at least one liquid fatty phase.
6. The process according to claim 5, wherein the at least one
liquid fatty phase comprises at least one volatile oil, and wherein
the composition has an evaporation profile such that the mass of
the at least one volatile oil evaporated after thirty minutes
ranges from 1.7 to 370 mg/cm.sup.2.
7. The process according to claim 6, wherein the composition has an
evaporation profile such that the mass of the at least one volatile
oil evaporated after thirty minutes ranges from 2 to 30
mg/cm.sup.2.
8. The process according to claim 5, wherein the liquid fatty phase
comprises at least one oil chosen from hydrocarbon-based volatile
oils containing from 8 to 16 carbon atoms and cyclic silicone
volatile oils.
9. The process according to claim 5, wherein the liquid fatty phase
is present in an amount ranging from 5% to 85% by weight, relative
to the total weight of the composition.
10. The process according to claim 9, wherein the liquid fatty
phase is present in an amount ranging from 15% to 60% by weight,
relative to the total weight of the composition.
11. The process according to claim 5, wherein the composition
further comprises at least one structuring agent for the liquid
fatty phase, chosen from waxes, semi-crystalline polymers and
lipophilic gelling agents.
12. The process according to claim 11, wherein the at least one
structuring agent is present in an amount ranging from 1% to 50% by
weight, relative to the total weight of the composition.
13. The process according to claim 12, wherein the at least one
structuring agent is present in an amount ranging from 7.5% to 17%
by weight, relative to the total weight of the composition.
14. The process according to claim 1, wherein the composition
comprises at least one wax chosen from structuring waxes and
non-structuring waxes.
15. The process according to claim 14, wherein the at least one
structuring wax is chosen from polar waxes and apolar waxes.
16. The process according to claim 14, wherein the at least one
non-structuring wax is chosen from polar waxes and apolar
waxes.
17. The process according to claim 14, wherein the composition
comprises at least one non-structuring wax and at least one
structuring wax in a structuring wax/non-structuring wax ratio
ranging from 5/95 to 50/50.
18. The process according to claim 17, wherein the structuring
wax/non-structuring wax ratio ranges from 15/85 to 35/65.
19. The process according to claim 14, wherein the at least one wax
chosen from structuring waxes and non-structuring waxes is present
in an amount ranging from 1% to 30% by weight, relative to the
total weight of the composition.
20. The process according to claim 19, wherein the at least one wax
chosen from structuring waxes and non-structuring waxes is present
in an amount ranging from 7.5% to 17% by weight, relative to the
total weight of the composition.
21. The process according to claim 1, wherein the composition
comprises at least one aprotic wax.
22. The process according to claim 21, wherein the at least one
aprotic wax is chosen from microcrystalline waxes, paraffin waxes
and polyethylene waxes.
23. The process according to claim 1, wherein the composition
comprises at least one protic wax.
24. The process according to claim 23, wherein the at least one
protic wax is chosen from beeswax and fatty alcohol waxes
containing from 20 to 60 carbon atoms.
25. The process according to claim 5, wherein the at least one
liquid fatty phase comprises at least one volatile
hydrocarbon-based oil chosen from isoparaffins containing from 8 to
16 carbon atoms, at least one polyethylene wax and at least one
fatty alcohol wax.
26. The process according to claim 5, wherein the at least one
liquid fatty phase comprises at least one volatile silicone oil
chosen from volatile cyclic silicone oils, at least one
polyethylene wax and at least one beeswax.
27. The process according to claim 26, wherein the at least one
volatile cyclic silicone oil has a viscosity.ltoreq.8 centistokes
(8.times.10.sup.-6 m.sup.2/s).
28. The process according to claim 1, wherein the composition
comprises at least one aqueous phase.
29. The process according to claim 1, wherein the composition
comprises at least one pasty compound.
30. The process according to claim 29, wherein the at least one
pasty compound is present in an amount ranging from 0.5% to 85% by
weight, relative to the total weight of the composition.
31. The process according to claim 30, wherein the at least one
pasty compound is present in an amount ranging from 5% to 15% by
weight, relative to the total weight of the composition
32. The process according to claim 1, wherein the composition
comprises at least one film-forming polymer.
33. The process according to claim 32, wherein the at least one
film-forming polymer is present in a solids content ranging from
0.1% to 30% by weight, relative to the total weight of the
composition.
34. The process according to claim 33, wherein the at least one
film-forming polymer is present in a solids content ranging from 1%
to 15% by weight, relative to the total weight of the
composition.
35. The process according to claim 1, wherein the composition
comprises at least one dyestuff.
36. The process according to claim 35, wherein the at least one
dyestuff is present in an amount ranging from 0.01% to 30% by
weight, relative to the total weight of the composition.
37. A process for coating keratin fibers, comprising: contacting
the keratin fibers with at least part of the surface of a stick of
a dry-applicable composition; and causing a relative displacement
between the surface of the stick of the dry-applicable composition
and the keratin fibers so as to bring about erosion the composition
and application to the keratin fibers in the form of a deposit of
at least one coat.
38. The process according to claim 37, wherein the dry-applicable
composition has a hardness ranging from 500 to 18,200 Pa.
39. The process according to claim 38, wherein the dry-applicable
composition has a hardness ranging from 1800 to 8200 Pa.
Description
[0001] This application claims benefit of U.S. Provisional
Application No. 60/704,423, filed Aug. 2, 2005, the contents of
which are incorporated herein by reference. This application also
claims benefit of priority under 35 U.S.C. .sctn. 119 to French
Patent Application No. FR 05 52287, filed Jul. 22, 2005, the
contents of which are also incorporated herein by reference.
[0002] The present disclosure relates to a process for coating
keratin fibers, such as the eyelashes, comprising applying a
particular composition to the keratin fibers.
[0003] The term "keratin fibers," as used herein, means the
eyelashes, the eyebrows, body hairs or head hair.
[0004] The composition may be in the form of a mascara or a product
for the eyebrows. In at least one embodiment of the present
disclosure, the composition is in the form of a mascara.
[0005] In the context of the present disclosure, the term "mascara"
means a composition intended to be applied to the eyelashes. The
mascara may be an eyelash makeup composition, an eyelash makeup
base (also known as a base coat), a composition to be applied over
a mascara, also known as a top coat, or a cosmetic composition for
treating the eyelashes. In at least one embodiment, the mascara is
used for human eyelashes, but the mascara may also be used for
false eyelashes in other embodiments.
[0006] Known eyelash makeup compositions or mascaras comprise at
least one wax or a mixture of waxes dispersed in an aqueous liquid
phase or organic solvent. They generally have a pasty texture and
are packaged in a container comprising a reservoir equipped with a
drainer and an applicator, for example in the form of a brush or a
comb, and are applied by taking up product from the reservoir using
the applicator, passing the applicator through the drainer to
remove the surplus product, and then placing the applicator
impregnated with mascara in contact with the eyelashes.
[0007] Mascaras in solid form, also known as "cake mascaras," which
are compositions comprising a high proportion of waxes, pigments
and surfactants, which can be broken down with water, i.e., before
being applied to the eyelashes, need to be placed in contact with
an aqueous phase so as to partially dissolve the mascara cake, and
are disclosed, for example in U.S. Pat. No. 2,007,245 and French
Patent No. 2 833 163. When using cake mascaras, the application is
made with a brush impregnated with water, which is placed in
contact with the mascara and the mixture taken up is then applied
to the eyelashes with the brush so as to deposit material onto the
eyelashes.
[0008] Thus, the present disclosure relates to another formulation
route for a composition for coating keratin fibers, such as the
eyelashes, which may allow quick, direct and/or practical
application to the eyelashes, without the use of a brush (direct
transfer of material onto the eyelashes), and which is
dry-applicable.
[0009] The term "dry-applicable," as used herein, means that the
composition is capable of forming on keratin fibers a deposit, that
can adhere and coat the fibers, without requiring any prior contact
with an aqueous phase, as opposed to cake mascaras, which are
erodable with water and must be partially dissolved beforehand in
order to be applied to the fibers and form an adherent and coating
deposit.
[0010] The composition used in the process according to the present
disclosure may also have at least one good staying power property
(e.g., water resistance and wear resistance) and may provide a
substantial and uniform deposit of material on the eyelashes.
[0011] More specifically, the present disclosure relates to a
process for coating keratin fibers, comprising the application to
the keratin fibers at least one coat of at least one composition in
the form of a stick, wherein the composition is dry-applicable.
[0012] According to another aspect, the present disclosure relates
to a process for coating keratin fibers, comprising placing the
fibers in contact with at least part of the surface of a stick of a
dry-applicable composition; and causing a relative displacement
between the surface of the stick and the fibers so as to bring
about erosion of the composition and its application to the fibers
in the form of a deposit of at least one coat.
[0013] As used herein, the term "stick" denotes a wand of
predetermined form, such as cylindrical, which, in the absence of a
constraint, at room temperature and atmospheric pressure, remains
in its predetermined form. Thus packaged in the form of a stick,
the composition may be self-supporting, such as for at least 60
seconds. Such sticks may be obtained, for example, by hot-casting
the composition in a mold. The sticks may also be obtained by
extrusion.
[0014] In at least one embodiment, the composition packaged in
stick form has a hardness ranging from 500 to 18,200 Pa.
[0015] In at least one further embodiment, the composition has a
hardness ranging from 900 to 10,000 Pa, such as from 1800 to 8200
Pa.
[0016] With such a hardness, the texture may be "soft" enough to
allow direct and easy application to the eyelashes, such as a
deposit of material by simply placing the composition in contact
with the eyelashes, without exerting undue pressure on the eyelash
fringe.
[0017] To determine the hardness of a stick in accordance with the
present disclosure, the "cheese wire" method may be used, which
comprises cutting the stick transversely using a rigid tungsten
wire 250 .mu.m in diameter, by advancing the wire relative to the
stick at a speed of 100 mm/min. The hardness corresponds to the
maximum shear force exerted by the wire on the stick at 20.degree.
C., this force being measured using a DFGS2 tensile testing machine
sold by the company Indelco-Chatillon. The measurement is repeated
6 times and the mean is then determined. The mean of the 6 values
read using the tensile testing machine mentioned above, which is
noted Y, is given in grams. This mean value is converted into
pascals by means of the equation below, to obtain the hardness
value: (Y.times.10.sup.-3.times.9.8)/area of the transverse section
of the stick (in m.sup.2).
[0018] In the case of a cylindrical stick of circular cross
section, the area of the transverse section is equal to
.pi..times.R.sup.2, R being the radius of the stick expressed in
meters.
[0019] According to this method, the hardness of a cosmetic
composition in accordance with at least one embodiment of the
present disclosure presented in stick form ranges, to within 10%,
from 500 to 18,200 Pa, such as, for example, from 900 to 10,000 Pa
or from 1800 to 8200 Pa.
[0020] The composition used in the process according to the present
disclosure may comprise a liquid fatty phase and at least one agent
for structuring the liquid fatty phase, via which the hardness of
the composition is adjusted.
Liquid Fatty Phase
[0021] For the purposes of the present disclosure, the term "liquid
fatty phase" means a fatty phase that is liquid at room temperature
(25.degree. C.) and atmospheric pressure (760 mmHg), composed of at
least one mutually compatible non-aqueous fatty substance that is
liquid at room temperature, also known as an oil.
[0022] The at least one oil may be chosen from volatile oils and/or
non-volatile oils, and mixtures thereof.
[0023] The at least one oil may be present in the composition
according to at least one embodiment of the present disclosure in
an amount ranging from 5% to 85% by weight, such as, for example,
from 10% to 70% or from 15% to 60% by weight, relative to the total
weight of the composition.
[0024] For the purposes of the present disclosure, the term
"volatile oil" means an oil that is capable of evaporating on
contact with the skin or the keratin fiber in less than one hour,
at room temperature and atmospheric pressure. Volatile organic
solvents and volatile oils according to the present disclosure are
volatile organic solvents and cosmetic oils that are liquid at room
temperature, with a non-zero vapor pressure at room temperature and
atmospheric pressure, for example, ranging from 0.13 Pa to 40,000
Pa (10.sup.-3 to 300 mmHg), from 1.3 Pa to 13,000 Pa (0.01 to 100
mmHg), or from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). As used herein,
the term "non-volatile oil" means an oil that remains on the skin
or the keratin fiber at room temperature and atmospheric pressure
for at least several hours and, for example, has a vapor pressure
of less than 10.sup.-3 mmHg (0.13 Pa).
[0025] In at least one embodiment, these oils may be chosen from
hydrocarbon-based oils, silicone oils or fluoro oils, or mixtures
thereof.
[0026] In the context of the present disclosure, the term
"hydrocarbon-based oil" means an oil mainly containing hydrogen and
carbon atoms and optionally oxygen, nitrogen, sulfur or phosphorus
atoms. The volatile hydrocarbon-based oils may be chosen from
hydrocarbon-based oils containing from 8 to 16 carbon atoms, such
as branched C.sub.8-C.sub.16 alkanes, for instance C.sub.8-C.sub.16
isoalkanes of petroleum origin (also known as isoparaffins), for
instance isododecane (also known as 2,2,4,4,6-pentamethylheptane),
isodecane and isohexadecane, for example the oils sold under the
trade names ISOPAR or PERMETHYL, branched C.sub.8-C.sub.16 esters
and isohexyl neopentanoate, and mixtures thereof. Other volatile
hydrocarbon-based oils, for instance petroleum distillates,
including those sold under the name SHELL SOLT by the company
Shell, may also be used. In at least one embodiment of the present
disclosure, the volatile solvent may be chosen from volatile
hydrocarbon-based oils containing from 8 to 16 carbon atoms, and
mixtures thereof.
[0027] Among volatile oils that may also be used according to the
present disclosure, non-limiting mention may be made of volatile
silicones, for instance volatile linear or cyclic silicone oils,
including those with a viscosity.ltoreq.8 centistokes
(8.times.10.sup.-6 m.sup.2/s) and those containing from 2 to 7
silicon atoms, these silicones optionally comprising alkyl or
alkoxy groups containing from 1 to 10 carbon atoms. Among volatile
silicone oils that may be used according to at least one embodiment
of the disclosure, non-limiting mention may be made of
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane and
dodecamethylpentasiloxane, and mixtures thereof.
[0028] Non-limiting mention may also be made of the linear volatile
alkyltrisiloxane oils of formula (I): ##STR1## wherein R is chosen
from alkyl groups comprising 2 to 4 carbon atoms and of which at
least one hydrogen atom may be substituted with at least one
fluorine or chlorine atom.
[0029] Among the oils of formula (I) that may be used according to
at least one embodiment of the present disclosure, non-limiting
mention may be made of: [0030]
3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, [0031]
3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and [0032]
3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, corresponding to the
oils of formula (I) wherein R is, respectively, a butyl group, a
propyl group and an ethyl group.
[0033] Volatile fluorinated solvents such as
nonafluoromethoxybutane or perfluoromethylcyclopentane may also be
used.
[0034] According to at least one embodiment, the composition
comprises a volatile oil or a mixture of volatile oils, or a
volatile liquid fatty phase, having in the composition an
evaporation profile such that the mass of volatile oil(s)
evaporated after thirty minutes ranges from 1.7 to 370 mg/cm.sup.2,
such as, for example, from 2 to 70 mg/cm.sup.2 or from 2 to 30
mg/cm.sup.2.
[0035] The evaporation profile is measured according to the
following protocol:
[0036] 15 g of oil or of the mixture of oils to be tested are
placed in a crystallizing dish (diameter: 7 cm) placed on a balance
which is in a chamber of about 0.3 m.sup.2 with controlled
temperature (25.degree. C.) and hygrometry (50% relative humidity).
The liquid is left to evaporate freely, without stirring,
ventilation being provided using a fan (Papst-Motoren, reference
8550 N, spinning at 2700 rpm) placed vertically above the
crystallizing dish containing the solvent, the vanes being directed
towards the crystallizing dish and 20 cm away from the base of the
crystallizing dish. The mass of oil(s) remaining in the
crystallizing dish is measured at regular intervals, such as every
30 minutes. The evaporation rates are expressed as mg of oil
evaporated per unit area (cm.sup.2) and per unit of time
(minutes).
[0037] In at least one embodiment, the composition comprises at
least one volatile oil chosen from hydrocarbon-based volatile oils
containing from 8 to 16 carbon atoms, volatile silicone oils
containing from 2 to 7 silicon atoms, and mixtures thereof.
[0038] The composition may also comprise at least one non-volatile
oil, chosen, for example, from non-volatile hydrocarbon-based oils
and/or silicone oils and/or fluoro oils.
[0039] Among non-volatile hydrocarbon-based oils that may be used
according to at least one embodiment of the present disclosure,
non-limiting mention may be made of:
[0040] hydrocarbon-based oils of plant origin, such as triesters of
fatty acids and of glycerol, the fatty acids of which may have
varied chain lengths from C.sub.4 to C.sub.24, these chains
possibly being linear or branched, and saturated or unsaturated;
these oils may be chosen from, for example, wheatgerm oil,
sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot
oil, castor oil, shea oil, avocado oil, olive oil, soybean oil,
sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut
oil, macadamia oil, jojoba oil, alfalfa oil, poppyseed oil, pumpkin
oil, marrow oil, blackcurrant oil, evening primrose oil, millet
oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil,
passionflower oil and musk rose oil; or caprylic/capric acid
triglycerides, for instance those sold by the company Stearineries
Dubois or those sold under the names MIGLYOL 810, 812 and 818 by
the company Dynamit Nobel;
[0041] synthetic ethers comprising 10 to 40 carbon atoms;
[0042] linear and branched hydrocarbons of mineral or synthetic
origin, such as petroleum jelly, polydecenes, hydrogenated
polyisobutene such as parleam, and squalane, and mixtures
thereof;
[0043] synthetic esters, for instance oils of formula
R.sub.1COOR.sub.2 wherein R.sub.1 is chosen from linear and
branched fatty acid residues comprising 1 to 40 carbon atoms and
R.sub.2 is chosen from hydrocarbon-based chains, which may be
branched, containing from 1 to 40 carbon atoms, on condition that
R.sub.1+R.sub.2.gtoreq.10 carbon atoms, for instance purcellin oil
(cetostearyl octanoate), isopropyl myristate, isopropyl palmitate,
C.sub.12 to C.sub.15 alkyl benzoates, hexyl laurate, diisopropyl
adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl
isostearate, alcohol or polyalcohol octanoates, decanoates or
ricinoleates, for instance propylene glycol dioctanoate;
hydroxylated esters, for instance isostearyl lactate or
diisostearyl malate; and pentaerythritol esters;
[0044] fatty alcohols that are liquid at room temperature with a
branched and/or unsaturated carbon-based chain containing from 12
to 26 carbon atoms, for instance octyldodecanol, isostearyl
alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or
2-undecylpentadecanol;
[0045] higher fatty acids such as oleic acid, linoleic acid or
linolenic acid;
[0046] carbonates;
[0047] acetates;
[0048] citrates;
[0049] and mixtures thereof.
[0050] Non-volatile silicone oils that may be used in the
composition according to the present disclosure may be non-volatile
polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising
alkyl or alkoxy groups, which are pendent and/or at the end of a
silicone chain, these groups each containing from 2 to 24 carbon
atoms, phenyl silicones, for instance phenyl trimethicones, phenyl
dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl
dimethicones, diphenylmethyldiphenyltrisiloxanes and
2-phenylethyltrimethylsiloxysilicates.
[0051] In at least one embodiment, fluoro oils that may be used in
the present disclosure may be chosen from fluorosilicone oils,
fluoro polyethers and fluorosilicones as described in European
Patent No. EP-A-0 847 752.
[0052] According to at least one embodiment, the fatty phase may
comprise an ester oil. This ester oil may be chosen from the esters
of monocarboxylic acids with monoalcohols and polyalcohols.
[0053] In at least one embodiment, the ester is chosen from
compounds of formula (II) below: R.sub.1--CO--O--R.sub.2 (II)
[0054] wherein:
[0055] R.sub.1 is chosen from linear and branched alkyl radicals of
1 to 40 carbon atoms, for example 7 to 19 carbon atoms, optionally
comprising at least one ethylenic double bond, and optionally
substituted, and
[0056] R.sub.2 is chosen from linear and branched alkyl radicals of
1 to 40 carbon atoms, for example 3 to 30 carbon atoms or 3 to 20
carbon atoms, optionally comprising at least one ethylenic double
bond, and optionally substituted.
[0057] The term "optionally substituted," as used herein, means
that R.sub.1 and/or R.sub.2 can comprise at least one substitutent
chosen, for example, from groups comprising at least one hetero
atom chosen from O, N and S, such as amino, amine, alkoxy and
hydroxyl.
[0058] In at least one embodiment, the total number of carbon atoms
of R.sub.1+R.sub.2 is .gtoreq.9.
[0059] R.sub.1 may be chosen from residues of linear and branched
fatty acids, including higher fatty acids, containing from 1 to 40,
for example, from 7 to 19 carbon atoms, and R.sub.2 may be chosen
from linear and branched hydrocarbon-based chains containing from 1
to 40, such as, for example, from 3 to 30 or from 3 to 20 carbon
atoms. In at least one embodiment, the number of carbon atoms of
R.sub.1+R.sub.2.gtoreq.9.
[0060] Non-limiting examples of groups R.sub.1 include those
derived from fatty acids chosen from acetic acid, propionic acid,
butyric acid, caproic acid, caprylic acid, pelargonic acid, capric
acid, undecanoic acid, lauric acid, myristic acid, palmitic acid,
stearic acid, isostearic acid, arachidic acid, behenic acid, oleic
acid, linolenic acid, linoleic acid, oleostearic acid, arachidonic
acid and erucic acid, and mixtures thereof.
[0061] Non-limiting examples of esters include purcellin oil
(cetostearyl octanoate), isononyl isononanoate, isopropyl
myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate,
2-octyldodecyl erucate, isostearyl isostearate, and heptanoates,
octanoates, decanoates or ricinoleates of alcohols or polyalcohols,
for example of fatty alcohols.
[0062] In at least one embodiment, the esters are chosen from the
compounds of formula (I) above, wherein R.sub.1 is chosen from
unsubstituted linear and branched alkyl groups of 1 to 40 carbon
atoms, such as 7 to 19 carbon atoms, optionally comprising at least
one ethylenic double bond, and R.sub.2 is chosen from unsubstituted
linear and branched alkyl group of 1 to 40 carbon atoms, such as 3
to 30 carbon atoms or 3 to 20 carbon atoms, optionally comprising
at least one ethylenic double bond.
[0063] In at least one embodiment, R.sub.1 is chosen from
unsubstituted branched alkyl groups of 4 to 14 carbon atoms, for
example 8 to 10 carbon atoms, and R.sub.2 is chosen from
unsubstituted branched alkyl groups of 5 to 15 carbon atoms, such
as 9 to 11 carbon atoms. In at least one embodiment of the present
disclosure, in formula (I), R.sub.1--CO-- and R.sub.2 have the same
number of carbon atoms and are derived from the same radical, such
as an unsubstituted branched alkyl, for example isononyl, i.e.,
wherein the ester oil molecule is symmetrical.
[0064] In at least one embodiment of the present disclosure, the
ester oil is chosen from the following compounds:
[0065] isononyl isononanoate,
[0066] cetostearyl octanoate,
[0067] isopropyl myristate,
[0068] 2-ethylhexyl palmitate,
[0069] 2-octyldodecyl stearate,
[0070] 2-octyldodecyl erucate,
[0071] isostearyl isostearate,
[0072] and mixtures thereof.
[0073] The liquid fatty phase may be present in an amount ranging
from 5% to 85% by weight, such as from 10% to 70% or from 15% to
60% by weight, relative to the total weight of the composition.
Structuring Agent
[0074] The composition according to the present disclosure may
comprise at least one agent for structuring the liquid fatty phase
(formed from the volatile or non-volatile organic solvents or oils
described above), chosen from waxes, semi-crystalline polymers and
lipophilic gelling agents, and mixtures thereof.
[0075] The structuring agent may be present in an amount ranging
from 1% to 50% by weight, such as, for example, from 5% to 20% or
from 7.5% to 17% by weight, relative to the total weight of the
composition.
[0076] The amount of oily structuring agent may be adjusted by a
person skilled in the art as a function of the structuring
properties of the agents.
Wax
[0077] In the context of the present disclosure, a wax is defined
as a lipophilic compound that is solid at room temperature
(25.degree. C.) which may or may not be deformable, with a
solid/liquid reversible change of state, having a melting point of
greater than or equal to 30.degree. C., which may be up to
200.degree. C., and, for example, may be up to 120.degree. C.
[0078] By bringing the wax to the liquid form (melting), it may be
possible to make it miscible with oils and to form a
microscopically uniform mixture, but on cooling the mixture to room
temperature, recrystallization of the wax in the oils of the
mixture may be obtained.
[0079] In at least one embodiment, waxes that are suitable for the
present disclosure may have a melting point of greater than or
equal to 45.degree. C., such as greater than or equal to 55.degree.
C.
[0080] For the purposes of the present disclosure, the melting
point corresponds to the temperature of the most endothermic peak
observed by thermal analysis (DSC) as described in ISO standard
11357-3; 1999. The melting point of the wax may be measured using a
differential scanning calorimeter (DSC), for example the
calorimeter sold under the name MDSC 2920 by the company TA
Instruments.
[0081] The measuring protocol is as follows:
[0082] A sample of 5 mg of wax placed in a crucible is subjected to
a first temperature rise ranging from -20.degree. C. to 100.degree.
C., at a heating rate of 10.degree. C./minute. It is then cooled
from 100.degree. C. to -20.degree. C. at a cooling rate of
100.degree. C./minute and is finally subjected to a second
temperature increase ranging from -20.degree. C. to 100.degree. C.
at a heating rate of 5.degree. C./minute. During the second
temperature increase, the variation of the difference in power
absorbed by the empty crucible and by the crucible containing the
sample of wax is measured as a function of the temperature. The
melting point of the compound is the temperature value
corresponding to the top of the peak of the curve representing the
variation in the difference in absorbed power as a function of the
temperature.
[0083] Waxes that may be used in the compositions according to at
least one embodiment of the disclosure are chosen from waxes that
are solid at room temperature of animal, plant, mineral or
synthetic origin, and mixtures thereof.
[0084] Waxes that may be used in the compositions according to at
least one embodiment of the disclosure have a hardness ranging from
0.5 MPa to 15 MPa, such as, for example, from 1 MPa to 15 MPa.
[0085] The hardness is determined by measuring the compression
force, measured at 20.degree. C. using the texturometer sold under
the name TA-XT2 by the company Rheo, equipped with a
stainless-steel cylindrical spindle 2 mm in diameter, travelling at
a measuring speed of 0.1 mm/second, and penetrating the wax to a
penetration depth of 0.3 mm.
[0086] The measuring protocol is as follows:
[0087] The wax is melted at a temperature equal to the melting
point of the wax +10.degree. C. The molten wax is poured into a
container 25 mm in diameter and 20 mm deep. The wax is
recrystallized at room temperature (25.degree. C.) for 24 hours
such that the surface of the wax is flat and smooth, and the wax is
then stored for at least 1 hour at 20.degree. C. before measuring
the hardness or the tack.
[0088] The texturometer spindle is displaced at a speed of 0.1 mm/s
then penetrates the wax to a penetration depth of 0.3 mm. When the
spindle has penetrated the wax to a depth of 0.3 mm, the spindle is
held still for 1 second (corresponding to the relaxation time) and
is then withdrawn at a speed of 0.5 mm/s.
[0089] The hardness value is the maximum compression force measured
divided by the area of the texturometer cylinder in contact with
the wax.
[0090] The composition may comprise at least one wax chosen from:
[0091] "structuring" waxes that have little affinity for the liquid
fatty phase of the composition, [0092] "non-structuring" waxes that
have affinity for the liquid fatty phase of the composition, [0093]
and mixtures thereof.
[0094] The "structuring" or "non-structuring" nature of the wax is
defined from the hardness value obtained on a binary mixture
consisting of 15% wax and 85% of the oil(s) of the liquid fatty
phase of the composition.
[0095] The hardness of the binary mixture is measured according to
the following protocol:
[0096] The wax is melted at a temperature about 10.degree. C. above
the melting point of the wax, with stirring using a magnetic bar,
and, after the wax has totally melted, the oil(s) is (are) then
added. Stirring with the magnetic bar is continued for 30
minutes.
[0097] The mixture is poured into an aluminum mold preheated to
42.degree. C. and left to stand for 10 minutes at 25.degree. C.,
the assembly is placed at -28.degree. C. for 20 minutes and is then
removed from the mold and packaged in packaging 12.3 mm in
diameter, which is kept at a temperature of 20.degree. C. for 24
hours before performing the measurement.
[0098] The hardness is measured using the "cheese wire" method,
which comprises cutting the stick transversely using a rigid
tungsten wire 250 .mu.m in diameter, by advancing the wire relative
to the stick at a speed of 100 mm/min. The hardness corresponds to
the maximum shear force exerted by the wire on the stick at
20.degree. C., this force being measured using a DFGS2 tensile
testing machine sold by the company Indelco-Chatillon. The
measurement is repeated 6 times and the mean is then determined.
The hardness is expressed in grams.
[0099] A wax whose binary mixture as defined above has a hardness
of greater than or equal to 35 g (.+-.2 g) is considered as
structuring.
[0100] In contrast, a wax whose binary mixture as defined above has
a hardness of less than 35 g (.+-.2 g) is considered as
non-structuring.
[0101] The hardness of the composition may be modified by
appropriately selecting the structuring and non-structuring waxes
as a function of the hardness of the wax-oil binary mixture.
[0102] In at least one embodiment, the composition comprises at
least one structuring wax and at least one non-structuring wax,
which may be present in a structuring wax/non-structuring wax ratio
ranging from 5/95 to 50/50, such as, for example, from 10/90 to
40/60 or from 15/85 to 35/65.
[0103] In at least one embodiment, the structuring and/or
non-structuring waxes may be chosen from protic waxes and aprotic
waxes, and mixtures thereof.
Aprotic Wax
[0104] As used herein, the term "aprotic wax" means a wax
comprising few or no hydrogen atoms linked to a highly
electronegative atom such as O or N.
[0105] In at least one embodiment, aprotic waxes are chosen from
apolar waxes, i.e., waxes consisting solely of molecules comprising
only carbon and hydrogen atoms in their chemical structure, in
other words comprising no hetero atoms (such as O, N or P).
[0106] Non-limiting examples of aprotic waxes, including apolar
waxes, which may be mentioned include paraffin waxes,
microcrystalline waxes, ozokerite, ceresin and synthetic waxes, for
instance polymethylene wax, polyethylene wax, propylene wax and
ethylene/propylene copolymers thereof, or alternatively
Fischer-Tropsch waxes, and mixtures thereof.
[0107] The waxes obtained by esterification or modified by
esterification and which may comprise residual OH groups as a
function of the esterification yield may be considered as aprotic
within the meaning of the present disclosure. Such waxes are, for
example, the wax obtained from the reaction of a fatty acid with a
branched polyol of bis(trimethylol) type, for instance those sold
under the name HEST by the company Heterene. Non-limiting mention
may also be made of silicone-modified waxes, for instance the
silicone-treated candelilla wax sold by Koster Keunen under the
name Siliconyl candelilla.
[0108] The waxes obtained by catalytic hydrogenation of animal or
plant oils containing linear or branched C.sub.8-C.sub.32 fatty
chains, such as hydrogenated jojoba oil, hydrogenated sunflower oil
or hydrogenated coconut oil, or the wax obtained by hydrogenation
of olive oil esterified with stearyl alcohol, may also be
considered as aprotic.
[0109] In at least one embodiment of the present disclosure, the
aprotic wax is chosen from microcrystalline waxes, paraffin waxes,
polyethylene waxes, including the wax sold under the reference Wax
AC 617 by the company Honeywell, and mixtures thereof.
Protic Wax
[0110] Waxes that are considered protic waxes are hydrocarbon-based
waxes, for instance beeswax or lanolin wax; orange wax, lemon wax,
rice bran wax, carnauba wax, candelilla wax, ouricurry wax, Japan
wax, berry wax, shellac wax and sumach wax; montan wax,
hydrogenated castor oil, hydrogenated lanolin oil, the waxes
obtained from the reaction of fatty acids with carbohydrates, for
instance disaccharides of sucrose type, such as sucrose
polybehenate, sold by Croda under the name CROMADERM B, and hydroxy
ester waxes, for instance C.sub.20-C.sub.40 alkyl
(hydroxystearyloxy)stearate wax, such as those sold under the names
"Kester Wax K 82 P.RTM." and "Kester Wax K 80 P.RTM." by the
company Koster Keunen. Non-limiting mention may also be made of
fatty alcohol waxes chosen from saturated and unsaturated, branched
and unbranched fatty alcohols containing from 20 to 60 carbon atoms
or mixtures comprising at least 30% of the fatty alcohols, for
example with polyethylene, for instance the wax sold under the
reference Performacol.RTM. 550 L by the company New Phase
Technologies.
[0111] In at least one embodiment, the protic wax is chosen from
beeswax and fatty alcohol waxes containing from 20 to 60 carbon
atoms, and mixtures thereof.
[0112] According to at least one embodiment, the composition
according to the present disclosure comprises at least one protic
wax, which is, for example, a polar wax, and at least one aprotic
wax, which is for example, an apolar wax, chosen from the waxes
mentioned above.
[0113] According to at least one embodiment of the present
disclosure, the composition comprises at least one liquid fatty
phase comprising at least one volatile hydrocarbon-based oil chosen
from isoparaffins containing from 8 to 16 carbon atoms, such as,
for example, isododecane, at least one aprotic wax, chosen, for
example, from polyethylene waxes, which is non-structuring, and at
least one polar wax chosen from fatty alcohol waxes, which is
structuring.
[0114] According to at least one other embodiment of the present
disclosure, the composition comprises at least one liquid fatty
phase comprising at least one volatile silicone oil chosen from
volatile cyclic silicone oils, such as those with a
viscosity.ltoreq.8 centistokes (8.times.10.sup.-6 m.sup.2/s), and,
for example, cyclopentadimethylsiloxane, at least one aprotic wax,
which may be apolar, chosen from polyethylene wax, which is
structuring on account of its affinity for silicone oils, and at
least one protic wax, which may be polar, chosen from beeswax,
which is non-structuring.
[0115] In at least one embodiment, the structuring and
non-structuring waxes may be present in an amount ranging from 1%
to 30% by weight, such as, for example, from 5% to 20% or from 7.5%
to 17% by weight, relative to the total weight of the
composition.
Semi-Crystalline Polymers
[0116] As used herein, the term "polymer" means compounds
containing at least two repeating units, for example at least three
repeating units or at least ten repeating units. In the context of
the present disclosure, the term "semi-crystalline polymer" means
polymers comprising a crystallizable portion, a crystallizable side
chain or a crystallizable block in the skeleton, and an amorphous
portion in the skeleton and having a first-order reversible
phase-change temperature, such as melting (solid-liquid
transition). When the crystallizable portion is in the form of a
crystallizable block of the polymer skeleton, the amorphous portion
of the polymer may be in the form of an amorphous block; in this
case, the semi-crystalline polymer is a block copolymer, for
example, of the diblock, triblock or multiblock type, comprising at
least one crystallizable block and at least one amorphous block. In
the present disclosure, the term "block" means at least five
identical repeating units. The crystallizable block is of chemical
nature different than that of the amorphous block.
[0117] The semi-crystalline polymer has a melting point of greater
than or equal to 30.degree. C. (e.g., ranging from 30.degree. C. to
80.degree. C.), and in at least one embodiment has a melting point
ranging from 30.degree. C. to 60.degree. C. This melting point is a
first-order change of state temperature.
[0118] The melting point may be measured by any known method, such
as using a differential scanning calorimeter (DSC).
[0119] In at least one embodiment, the semi-crystalline polymer has
a number-average molecular mass of greater than or equal to 1000.
In at least one further embodiment, the semi-crystalline polymer of
the composition of the present disclosure has a number-average
molecular mass Mn ranging from 2000 to 800,000, such as, for
example, from 3000 to 500,000, or from 4000 to 150,000, or it may
have a number-average molecular mass less than 100,000, such as
from 4000 to 99,000. In at least one embodiment, the
semi-crystalline polymer has a number-average molecular mass of
greater than 5600, for example ranging from 5700 to 99,000.
[0120] For the purposes of the present disclosure, the term
"crystallizable chain or block" means a chain or block which, if it
were alone, would reversibly change from the amorphous state to the
crystalline state, depending on whether the system is above or
below the melting point. For the purposes of the present
disclosure, a "chain" is a group of atoms, which is pendent or
lateral relative to the polymer skeleton. A "block" is a group of
atoms belonging to the skeleton, this group constituting one of the
repeating units of the polymer. In at least one embodiment, the
"crystallizable side chain" may be a chain containing at least six
carbon atoms.
[0121] The semi-crystalline polymer may be chosen from block
copolymers comprising at least one crystallizable block and at
least one amorphous block, and homopolymers and copolymers bearing
at least one crystallizable side chain per repeating unit, and
mixtures thereof.
[0122] Such polymers are described, for example, in European Patent
No. EP 1 396 259.
[0123] In at least one embodiment of the present disclosure, the
polymer is derived from a monomer containing a crystallizable chain
chosen from saturated C.sub.14-C.sub.22 alkyl (meth)acrylates.
[0124] As an example of a semi-crystalline polymer that may be used
in the composition according to the present disclosure,
non-limiting mention may be made of the Intelimer.RTM. products
from the company Landec described in the brochure "Intelimer.RTM.
Polymers", Landec IP22 (Rev. 4-97). These polymers are in solid
form at room temperature (25.degree. C.) and bear crystallizable
side chains.
Lipophilic Gelling Agents
[0125] Gelling agents that may be used in the compositions
according to the present disclosure may be organic or mineral,
polymeric or molecular lipophilic gelling agents.
[0126] Among mineral lipophilic gelling agents that may be used
according to at least one embodiment of the present disclosure,
non-limiting mention may be made of optionally modified clays, for
instance hectorites modified with a C.sub.10 to C.sub.22 fatty acid
ammonium chloride, for instance hectorite modified with
distearyldimethylammonium chloride, for instance the product sold
under the name Bentone 38V.RTM. by the company Elementis.
[0127] Non-limiting mention may also be made of fumed silica
optionally subjected to a hydrophobic surface treatment, the
particle size of which is less than 1 .mu.m. In at least one
embodiment, the surface of the silica may be chemically modified by
chemical reaction generating a reduced number of silanol groups
present at the surface of the silica. In at least one embodiment,
silanol groups can be substituted with hydrophobic groups: a
hydrophobic silica is then obtained. The hydrophobic groups may
be:
[0128] trimethylsiloxyl groups, which are obtained, for example, by
treating fumed silica in the presence of hexamethyldisilazane.
Silicas thus treated are known as "silica silylate" according to
the CTFA (6th edition, 1995). They are sold, for example, under the
references Aerosil R812.RTM. by the company Degussa, and Cab-O-Sil
TS-530.RTM. by the company Cabot;
[0129] dimethylsilyloxyl or polydimethylsiloxane groups, which are
obtained, for example, by treating fumed silica in the presence of
polydimethylsiloxane or dimethyldichlorosilane. Silicas thus
treated are known as "silica dimethyl silylate" according to the
CTFA (6th edition, 1995). They are sold, for example, under the
references Aerosil R9728 and Aerosil R974.RTM. by the company
Degussa, and Cab-O-Sil TS-610.RTM. and Cab-O-Sil TS-720.RTM. by the
company Cabot.
[0130] In at least one embodiment, the hydrophobic fumed silica has
a particle size that may be nanometric to micrometric, for example
ranging from about 5 to 200 nm.
[0131] It is also possible to use non-polymeric, molecular organic
gelling agents, also known as organogelling agents, associated with
a liquid fatty phase (which may be the liquid fatty phase of the
composition according to the present disclosure), which are
compounds whose molecules are capable of establishing between
themselves physical interactions leading to self-aggregation of the
molecules with formation of a supramolecular 3D network that is
responsible for the gelation of the liquid fatty phase.
[0132] The supramolecular network may result from the formation of
a network of fibrils (caused by the stacking or aggregation of
organogelling molecules), which immobilizes the molecules of the
liquid fatty phase.
[0133] The ability to form this network of fibrils, and thus to
gel, depends on the nature (or chemical class) of the organogelling
agent, on the nature of the substitutents borne by its molecules
for a given chemical class, and on the nature of the liquid fatty
phase.
[0134] The physical interactions are of diverse nature but exclude
co-crystallization. These physical interactions may be, for
example, interactions of self-complementary hydrogen interaction
type, .pi. interactions between unsaturated rings, dipolar
interactions, coordination bonds with organometallic derivatives,
and combinations thereof. Each molecule of an organogelling agent
can establish several types of physical interaction with a
neighboring molecule. Thus, for example, the molecules of the
organogelling agents according to the present disclosure can
comprise at least one group capable of establishing hydrogen bonds,
such as, for example, at least two groups, at least one aromatic
ring, at least two aromatic rings, at least one ethylenically
unsaturated bonds and/or at least one asymmetric carbons. In at
least one embodiment, the groups capable of forming hydrogen bonds
are chosen from hydroxyl, carbonyl, amine, carboxylic acid, amide,
urea and benzyl groups, and combinations thereof.
[0135] Organogelling agents according to the present disclosure can
be soluble in the liquid fatty phase after heating to obtain a
transparent uniform liquid phase. They may be solid or liquid at
room temperature and atmospheric pressure.
[0136] Molecular organogelling agents that may be used in the
composition according to at least one embodiment of the present
disclosure may be chosen from those described in the document
"Specialist Surfactants" edited by D. Robb, 1997, pp. 209-263,
Chapter 8 by P. Terech, European Patent Application Nos. EP-A-1 068
854 and EP-A-1 086 945, or International Patent Application No. WO
02/47031.
[0137] Non-limiting mention may be made, among these organogelling
agents, of amides of carboxylic acids, such as tricarboxylic acids,
for instance cyclohexanetricarboxamides (see European Patent
Application No. EP-A-1 068 854), diamides with hydrocarbon-based
chains each containing from 1 to 22 carbon atoms, for example from
6 to 18 carbon atoms, the chains being unsubstituted or substituted
with at least one substitutent chosen from ester, urea and fluoro
groups (see European Patent Application No. EP-A-1 086 945) and
diamides resulting from the reaction of diaminocyclohexane, such as
diaminocyclohexane in trans form, and of an acid chloride, for
instance N,N'-bis(dodecanoyl)-1,2-diaminocyclohexane, N-acylamino
acid amides, for instance the diamides resulting from the action of
an N-acylamino acid with amines containing from 1 to 22 carbon
atoms, for instance those described in International Patent
Application No. WO 93/23008 and, for example, N-acylglutamic acid
amides wherein the acyl group is chosen from C.sub.8 to C.sub.22
alkyl chains, such as N-lauroyl-L-glutamic acid dibutylamide,
manufactured or sold by the company Ajinomoto under the name GP-1,
and mixtures thereof.
[0138] The polymeric organic lipophilic gelling agents are, for
example: [0139] partially or totally crosslinked elastomeric
organopolysiloxanes of three-dimensional structure, for instance
those sold under the names KSG6.RTM., KSG6.RTM. and KSG18.RTM. from
Shin-Etsu, Trefil E-505C.RTM. or Trefil E-506C.RTM. from Dow
Corning, Gransil SR-CYC.RTM., SR DMF 10.RTM., SR-DC556.RTM., SR
5CYC gel.RTM., SR DMF 10 gel.RTM. and SR DC 556 gel.RTM. from Grant
Industries and SF 1204.RTM. and JK 113.RTM. from General Electric;
[0140] ethylcellulose, for instance the product sold under the name
Ethocel.RTM. by Dow Chemical; [0141] polycondensates of polyamide
type resulting from condensation between (.alpha.) at least one
acid chosen from dicarboxylic acids containing at least 32 carbon
atoms, such as fatty acid dimers, and (.beta.) an alkylenediamine
and, for example, ethylenediamine, in which the polyamide polymer
comprises at least one carboxylic acid end group esterified or
amidated with at least one saturated and linear monoalcohol or one
saturated and linear monoamine containing from 12 to 30 carbon
atoms, and, for example, copolymers such as the products sold under
the Uniclear names by the company Arizona Chemical; [0142] silicone
polyamides of the polyorganosiloxane type such as those described
in U.S. Pat. Nos. 5,874,069, 5,919,441, 6,051,216 and 5,981,680,
for instance those sold under the reference Dow Corning 2-8179
GELLANT by the company Dow Corning; [0143] galactomannans
containing from one to six hydroxyl groups per saccharide, such as
from two to four hydroxyl groups per saccharide, substituted with a
saturated or unsaturated alkyl chain, for instance guar gum
alkylated with C.sub.1-C.sub.6 alkyl chains, such as
C.sub.1-C.sub.3 alkyl chains, and mixtures thereof; [0144]
optionally hydrogenated block copolymers, of "diblock", "triblock"
or "radial" type, such as those containing styrene blocks and
ethylene/C.sub.3-C.sub.4 alkylene blocks.
[0145] Among examples of diblock copolymers, which may be
hydrogenated, that may be used according to the present disclosure,
non-limiting mention may be made of styrene-ethylene/propylene
copolymers and styrene-ethylene/butadiene copolymers. Diblock
copolymers are sold, for example, under the name Kraton.RTM. G1701
E by the company Kraton Polymers.
[0146] Among examples of triblock copolymers, which may be
hydrogenated, that may be used according to the present disclosure,
non-limiting mention may be made of
styrene-ethylene/propylene-styrene copolymers,
styrene-ethylene/butadiene-styrene copolymers,
styrene-isoprene-styrene copolymers and styrene-butadiene-styrene
copolymers. Triblock polymers are sold, for example, under the
names Kraton.RTM. G1650, Kraton.RTM. G1652, Kraton.RTM. D1101,
Kraton.RTM. D1102 and Kraton.RTM. D1160 by the company Kraton
Polymers.
[0147] It is also possible to use a mixture of hydrogenated
styrene-butylene/ethylene-styrene triblock copolymer and of
hydrogenated ethylene-propylene-styrene star polymer, such a
mixture being, for example, in isododecane. Such mixtures are sold,
for example, by the company Penreco under the trade names
Versagel.RTM. M5960 and Versagel.RTM. M5670.
[0148] Non-limiting mention may also be made of
polystyrene/polyisoprene or polystyrene/polybutadiene copolymers
such as those sold under the name Luvitol HSB.RTM. by the company
BASF.
[0149] Among the lipophilic gelling agents that may be used in the
compositions according to the present disclosure, non-limiting
mention may also be made of fatty acid esters of dextrin, such as
dextrin palmitates, including the products sold under the name
Rheopearl TL.RTM. or Rheopearl KL.RTM. by the company Chiba
Flour.
Pasty Compound
[0150] In at least one embodiment, the composition according to the
present disclosure may comprise at least one pasty compound.
[0151] For the purposes of the present disclosure, the term "pasty"
denotes a lipophilic fatty compound that undergoes a reversible
solid/liquid change of state and that comprises, at a temperature
of 23.degree. C., a liquid fraction and a solid fraction.
[0152] In at least one embodiment, the pasty compound has a
hardness at 20.degree. C. ranging from 0.001 to 0.5 MPa, such as
from 0.002 to 0.4 MPa.
[0153] The hardness is measured according to a method of
penetration of a probe in a sample of compound and in particular
using a texture analyzer (for example the TA-XT21 machine from
Rheo) equipped with a stainless-steel cylinder 2 mm in diameter.
The hardness measurement is performed at 20.degree. C. at the
center of five samples. The cylinder is introduced into each sample
at a pre-speed of 1 mm/s and then at a measuring speed of 0.1 mm/s,
the penetration depth being 0.3 mm. The hardness value revealed is
that of the maximum peak.
[0154] This pasty compound may also, at a temperature of 23.degree.
C., be in the form of a liquid fraction and a solid fraction. In
other words, the starting melting point of the pasty compound may
be less than 23.degree. C. The liquid fraction of the pasty
compound measured at 23.degree. C. is present in an amount ranging
from 23% to 97% by weight of the compound. In at least one
embodiment, this liquid fraction at 23.degree. C. is present in an
amount ranging from 40% to 85% by weight of the compound.
[0155] The liquid fraction by weight of the pasty compound at
23.degree. C. is equal to the ratio of the heat of fusion consumed
at 23.degree. C. to the heat of fusion of the pasty compound.
[0156] The heat of fusion of the pasty compound is the heat
consumed by the compound to change from the solid state to the
liquid state. The pasty compound is said to be in the solid state
when all of its mass is in solid form. The pasty compound is said
to be in the liquid state when all of its mass is in liquid
form.
[0157] The heat of fusion of the pasty compound is equal to the
area under the curve of the thermogram obtained using a
differential scanning calorimeter (DSC), such as the calorimeter
sold under the name MDSC 2920 by the company TA Instrument, with a
temperature rise of 5 or 10.degree. C. per minute, according to
standard ISO 11357-3:1999. The heat of fusion of the pasty compound
is the amount of energy required to make the compound change from
the solid state to the liquid state. It is expressed in J/g.
[0158] The heat of fusion consumed at 23.degree. C. is the amount
of energy absorbed by the sample to change from the solid state to
the state that it has at 23.degree. C., comprising a liquid
fraction and a solid fraction.
[0159] In at least one embodiment, the liquid fraction of the pasty
compound, measured at 32.degree. C., ranges from 40% to 100% by
weight of the compound, such as, for example, from 50% to 100%,
from 80% to 100%, or from 90% to 100% by weight of the compound.
When the liquid fraction of the pasty compound measured at
32.degree. C. is equal to 100%, the temperature of the end of the
melting range of the pasty compound is less than or equal to
32.degree. C.
[0160] The liquid fraction of the pasty compound measured at
32.degree. C. is equal to the ratio of the heat of fusion consumed
at 32.degree. C. to the heat of fusion of the pasty compound. The
heat of fusion consumed at 32.degree. C. is calculated in the same
manner as the heat of fusion consumed at 23.degree. C.
[0161] In at least one embodiment, the pasty compound is chosen
from synthetic compounds and compounds of plant origin. A pasty
compound may be obtained by synthesis from starting materials of
plant origin.
[0162] According to at least one embodiment of the present
disclosure, the pasty compound is chosen from: [0163] lanolin and
derivatives thereof, [0164] polymer or non-polymer silicone
compounds, [0165] polymer or non-polymer fluoro compounds, [0166]
vinyl polymers, such as: [0167] olefin homopolymers [0168] olefin
copolymers [0169] hydrogenated diene homopolymers and copolymers
[0170] linear or branched oligomers, which are homopolymers or
copolymers of alkyl (meth)acrylates, including those containing a
C.sub.8-C.sub.30 alkyl group [0171] oligomers, which are
homopolymers and copolymers of vinyl esters containing
C.sub.8-C.sub.30 alkyl groups [0172] oligomers, which are
homopolymers and copolymers of vinyl ethers containing
C.sub.8-C.sub.30 alkyl groups,
[0173] liposoluble polyethers resulting from the polyetherification
between at least one C.sub.2-C.sub.100 diol, such as
C.sub.2-C.sub.50 diols,
[0174] esters and polyesters,
and mixtures thereof.
[0175] In at least one embodiment, the pasty compound is a polymer,
such as a hydrocarbon-based polymer.
[0176] At least one embodiment of the present disclosure comprises
asilicone and fluoro pasty compound that is polymethyl
trifluoropropyl methylalkyl dimethylsiloxane, sold under the name
X22-1088 by Shin-Etsu.
[0177] When the pasty compound is a silicone and/or fluoro polymer,
the composition may comprise a compatibilizer such as short-chain
esters, for instance isodecyl neopentanoate.
[0178] Among the liposoluble polyethers that may be used according
to at least one embodiment of the present disclosure, non-limiting
mention may be made of copolymers of ethylene oxide and/or of
propylene oxide with C.sub.6-C.sub.30 long-chain alkylene oxides,
including those copolymers such that the weight ratio of the
ethylene oxide and/or of the propylene oxide to the alkylene oxides
in the copolymer is from 5:95 to 70:30. In this family, further
non-limiting mention may be made of copolymers such that the
long-chain alkylene oxides are arranged in blocks with an average
molecular weight of from 1000 to 10,000, for example a
polyoxyethylene/polydodecyl glycol block copolymer such as the
ethers of dodecanediol (22 mol) and of polyethylene glycol (45 EO)
sold under the brand name ELFACOS ST9 by Akzo Nobel.
[0179] Among the esters that may be used according to at least one
embodiment of the present disclosure, non-limiting mention may be
made of:
[0180] esters of a glycerol oligomer, such as diglycerol esters,
including condensates of adipic acid and of glycerol, for which
some of the hydroxyl groups of the glycerols may have reacted with
a mixture of fatty acids such as stearic acid, capric acid, stearic
acid and isostearic acid and 12-hydroxystearic acid, for instance
those sold under the brand name SOFTISAN 649 by the company Sasol,
phytosterol esters,
[0181] pentaerythritol esters, esters formed from: [0182] at least
one alcohol, at least one of the alcohols being a Guerbet alcohol,
and [0183] a diacid dimer formed from at least one unsaturated
fatty acid, for instance the ester of fatty acid dimer of tall oil
containing 36 carbon atoms and of a mixture i) of Guerbet alcohols
containing 32 carbon atoms and ii) of behenyl alcohol; the ester of
linoleic acid dimer and of a mixture of two Guerbet alcohols,
2-tetradecyloctadecanol (32 carbon atoms) and 2-hexadecyleicosanol
(36 carbon atoms),
[0184] non-crosslinked polyesters resulting from polycondensation
between a linear or branched C.sub.4-C.sub.50 dicarboxylic acid or
polycarboxylic acid and a C.sub.2-C.sub.50 diol or polyol,
[0185] polyesters resulting from the esterification, with a
polycarboxylic acid, of an aliphatic hydroxycarboxylic acid ester,
for instance RISOCAST DA-L and RISOCAST DA-H sold by the Japanese
company Kokyu Alcohol Kogyo, which are esters resulting from the
esterification reaction of hydrogenated castor oil with dilinoleic
acid or isostearic acid,
[0186] aliphatic esters of an ester resulting from the
esterification of an aliphatic hydroxycarboxylic acid ester with an
aliphatic carboxylic acid; (SALACOS HCIS (V)-L sold by the company
Nishing Oil).
[0187] The aliphatic carboxylic acid contains from 4 to 30 carbon
atoms, such as from 8 to 30 carbon atoms. In at least one
embodiment, the aliphatic carboxylic acid is chosen from hexanoic
acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic
acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic
acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid,
hexyldecanoic acid, heptadecanoic acid, octadecanoic acid,
isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic
acid, octyldodecanoic acid, heneicosanoic acid and docosanoic acid,
and mixtures thereof.
[0188] In at least one embodiment, the aliphatic carboxylic acid is
branched.
[0189] According to at least one embodiment of the present
disclosure, the aliphatic hydroxycarboxylic acid ester is derived
from a hydroxylated aliphatic carboxylic acid containing from 2 to
40 carbon atoms, such as from 10 to 34 carbon atoms or from 12 to
28 carbon atoms, and from 1 to 20 hydroxyl groups, such as, for
example, from 1 to 10 hydroxyl groups or from 1 to 6 hydroxyl
groups. The aliphatic hydroxycarboxylic acid ester may be chosen
from:
a) partial or total esters of saturated linear monohydroxylated
aliphatic monocarboxylic acids;
b) partial or total esters of unsaturated monohydroxylated
aliphatic monocarboxylic acids;
c) partial or total esters of saturated monohydroxylated aliphatic
polycarboxylic acids;
d) partial or total esters of saturated polyhydroxylated aliphatic
polycarboxylic acids;
e) partial or total esters of C.sub.2 to C.sub.16 aliphatic polyols
that have reacted with a monohydroxylated or polyhydroxylated
aliphatic monocarboxylic or polycarboxylic acid, and mixtures
thereof.
[0190] The aliphatic esters of an ester according to at least one
embodiment may be chosen from:
[0191] the ester resulting from the esterification reaction of
hydrogenated castor oil with isostearic acid in proportions of 1 to
1 (1/1) or hydrogenated castor oil monoisostearate,
[0192] the ester resulting from the esterification reaction of
hydrogenated castor oil with isostearic acid in proportions of 1 to
2 (1/2) or hydrogenated castor oil diisostearate,
[0193] the ester resulting from the esterification reaction of
hydrogenated castor oil with isostearic acid in proportions of 1 to
3 (1/3) or hydrogenated castor oil triisostearate,
[0194] and mixtures thereof.
[0195] In at least one embodiment of the present disclosure, the
pasty compound is present in an amount ranging from 0.5% to 85% by
weight, such as, for example, from 1% to 60%, from 2% to 30%, or
from 5% to 15% by weight, relative to the total weight of the
composition.
Aqueous Phase
[0196] The composition according to at least one embodiment of the
present disclosure may comprise an aqueous phase, which may
comprise water or a mixture of water and of water-miscible solvent
(miscibility in water of greater than 50% by weight at 25.degree.
C.), for example lower monoalcohols containing from 1 to 5 carbon
atoms, such as ethanol or isopropanol, glycols containing from 2 to
8 carbon atoms, such as propylene glycol, ethylene glycol,
1,3-butylene glycol, or dipropylene glycol, C.sub.3-C.sub.4 ketones
and C.sub.2-C.sub.4 aldehydes, and mixtures thereof.
[0197] According to at least one embodiment, the composition
comprises an aqueous phase present in an amount less than 10% by
weight, such as, for example, less than 5% by weight or less than
2% by weight, relative to the total weight of the composition.
[0198] According to at least one other embodiment, the composition
comprises an aqueous phase in an amount ranging from 5% to 95% by
weight, such as, from 10% to 80% by weight or from 15% to 60% by
weight, relative to the total weight of the composition.
Emulsifying System
[0199] In at least one embodiment, the composition according to the
present disclosure may contain emulsifying surfactants in an amount
ranging from 0.01% to 30% by weight, such as, for example, from 1%
to 15% or from 2% to 10% by weight, relative to the total weight of
the composition.
[0200] According to at least one embodiment of the present
disclosure, an emulsifier appropriately chosen to obtain an
oil-in-water emulsion is used. In at least one further embodiment,
an emulsifier having at 25.degree. C. an HLB
(hydrophilic-lipophilic balance), in the Griffin sense, of greater
than or equal to 8 may be used.
[0201] The HLB value according to Griffin is defined in J. Soc.
Cosm. Chem. 1954 (volume 5), pages 249-256.
[0202] In at least one embodiment, these surfactants may be chosen
from nonionic, anionic, cationic and amphoteric surfactants or
combinations thereof. Reference may be made to the document
"Encyclopedia of Chemical Technology, Kirk-Othmer," volume 22, pp.
333-432, 3rd edition, 1979, Wiley, for the definition of the
properties and (emulsifying) functions of surfactants, including
pp. 347-377 of this reference, for anionic, amphoteric and nonionic
surfactants.
Hydrophilic Gelling Agent
[0203] In at least one embodiment, the composition according to the
present disclosure may comprise at least one hydrophilic gelling
agent when it comprises an aqueous phase.
[0204] According to at least one embodiment, hydrophilic gelling
agents that may be used in the compositions according to the
present disclosure may be chosen from:
[0205] homopolymers or copolymers of acrylic or methacrylic acid or
the salts and esters thereof, and, for example, the products sold
under the names Versicol F.RTM. or Versicol K.RTM. by the company
Allied Colloid, Ultrahold 8.RTM. by the company Ciba-Geigy, and the
polyacrylic acids of Synthalen K type;
[0206] copolymers of acrylic acid and of acrylamide sold in the
form of the sodium salt thereof under the name Reten.RTM. by the
company Hercules, sodium polymethacrylate sold under the name
Darvan 7.RTM. by the company Vanderbilt, and the sodium salts of
polyhydroxycarboxylic acids sold under the name Hydagen F.RTM. by
the company Henkel;
[0207] polyacrylic acid/alkyl acrylate copolymers of the Pemulen
type;
[0208] AMPS (polyacrylamidomethylpropanesulfonic acid partially
neutralized with ammonia and highly crosslinked) sold by the
company Clariant;
[0209] AMPS/acrylamide copolymers of the Sepigel.RTM. or
Simulgel.RTM. type, sold by the company SEPPIC, and
[0210] AMPS/polyoxyethylenated alkyl methacrylate copolymers
(crosslinked or non-crosslinked), and mixtures thereof.
[0211] The water-soluble film-forming polymers mentioned above may
also act as hydrophilic gelling agents.
[0212] In at least one embodiment, the at least one hydrophilic
gelling agent may be present in a solids content ranging from 0.01%
to 30% by weight, such as, for example, from 0.5% to 20% by weight
or from 1% to 15% by weight, relative to the total weight of the
composition.
Film-Forming Polymer
[0213] According to at least one embodiment, the composition
according to the present disclosure may comprise at least one
film-forming polymer.
[0214] The at least one film-forming polymer may be present in the
composition according to the disclosure in a solids (or active
material) content ranging from 0.1% to 30% by weight, such as, for
example, from 0.5% to 20% or from 1% to 15% by weight, relative to
the total weight of the composition.
[0215] In the present disclosure, the expression "film-forming
polymer" means a polymer that is capable, by itself or in the
presence of an auxiliary film-forming agent, of forming a
macroscopically continuous film that adheres to the eyelashes, such
as a cohesive film or a film whose cohesion and mechanical
properties are such that the film can be isolated and manipulated
separately, for example when the film is made by casting on a
non-stick surface, for instance a Teflon-coated or silicone-coated
surface.
[0216] Among the film-forming polymers that may be used in the
composition 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.
[0217] The expression "free-radical film-forming polymer," as used
herein, means a polymer obtained by polymerization of unsaturated,
including ethylenically unsaturated monomers, each monomer being
capable of homopolymerizing (unlike polycondensates).
[0218] The film-forming polymers of free-radical type may be, for
example, vinyl polymers or copolymers, including acrylic
polymers.
[0219] The vinyl film-forming polymers may result from the
polymerization of ethylenically unsaturated monomers containing at
least one acidic group and/or esters of these acidic monomers
and/or amides of these acidic monomers.
[0220] Monomers bearing an acidic group which may be used according
to at least one embodiment include .alpha.,.beta.-ethylenic
unsaturated carboxylic acids such as acrylic acid, methacrylic
acid, crotonic acid, maleic acid or itaconic acid. In at least one
further embodiment, (meth)acrylic acid and crotonic acid are used.
In at least one embodiment, (meth)acrylic acid is used.
[0221] According to at least one embodiment, the esters of acidic
monomers are chosen from (meth)acrylic acid esters (also known as
(meth)acrylates), including (meth)acrylates of an alkyl, such as a
C.sub.1-C.sub.30 or C.sub.1-C.sub.20 alkyl, (meth)acrylates of an
aryl, for example a C.sub.6-C.sub.10 aryl, and (meth)acrylates of a
hydroxyalkyl, such as a C.sub.2-C.sub.6 hydroxyalkyl.
[0222] Among the alkyl (meth)acrylates that may be used according
to at least one embodiment of the present disclosure, non-limiting
mention may be made of methyl methacrylate, ethyl methacrylate,
butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl
methacrylate, lauryl methacrylate and cyclohexyl methacrylate.
[0223] Among the hydroxyalkyl (meth)acrylates that may be used
according to at least one embodiment of the present disclosure,
non-limiting mention may be made of hydroxyethyl acrylate,
2-hydroxypropyl acrylate, hydroxyethyl methacrylate and
2-hydroxypropyl methacrylate.
[0224] Among the aryl (meth)acrylates that may be used according to
at least one embodiment of the present disclosure, non-limiting
mention may be made of benzyl acrylate and phenyl acrylate.
[0225] In at least one embodiment, the (meth)acrylic acid esters
are alkyl (meth)acrylates.
[0226] According to the present disclosure, the alkyl group of the
esters may be either fluorinated or perfluorinated, i.e., some or
all of the hydrogen atoms of the alkyl group are substituted with
fluorine atoms.
[0227] Non-limiting examples of amides of the acid monomers that
may be mentioned include (meth)acrylamides, such as
N-alkyl(meth)acrylamides, for example of a C.sub.2-C.sub.12 alkyl.
Among the N-alkyl(meth)acrylamides that may be used according to at
least one embodiment of the present disclosure, non-limiting
mention may be made of N-ethylacrylamide, N-t-butylacrylamide,
N-t-octylacrylamide and N-undecylacrylamide.
[0228] The vinyl film-forming polymers may also result from the
homopolymerization or copolymerization of monomers chosen from
vinyl esters and styrene monomers. In at least one embodiment,
these monomers may be polymerized with acid monomers and/or esters
thereof and/or amides thereof, such as those mentioned above.
[0229] Non-limiting examples of vinyl esters that may be mentioned
include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl
benzoate and vinyl t-butylbenzoate.
[0230] Non-limiting examples of styrene monomers that may be
mentioned include styrene and .alpha.-methylstyrene.
[0231] Among the film-forming polycondensates that may be used
according to at least one embodiment, non-limiting mention may be
made of polyurethanes, polyesters, polyesteramides, polyamides,
epoxyester resins and polyureas.
[0232] The polyurethanes may be chosen from anionic, cationic,
nonionic and amphoteric polyurethanes, polyurethane-acrylics,
polyurethane-polyvinylpyrrolidones, polyester-polyrethanes,
polyether-polyurethanes, polyureas and polyurea/polyurethanes, and
mixtures thereof.
[0233] The polyesters may be obtained, in a known manner, by
polycondensation of dicarboxylic acids with polyols, such as
diols.
[0234] The dicarboxylic acid may be aliphatic, alicyclic or
aromatic. Non-limiting examples of such acids that may be mentioned
include: oxalic acid, malonic acid, dimethylmalonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid,
2,2-dimethylglutaric acid, azeleic acid, suberic acid, sebacic
acid, fumaric acid, maleic acid, itaconic acid, phthalic acid,
dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic
acid, 2,5-norbornanedicarboxylic acid, diglycolic acid,
thiodipropionic acid, 2,5-naphthalenedicarboxylic acid or
2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers
may be used alone or as a combination of at least two dicarboxylic
acid monomers. Among these monomers, in at least one embodiment,
the monomers are chosen from phthalic acid, isophthalic acid and
terephthalic acid.
[0235] The diol may be chosen from aliphatic, alicyclic and
aromatic diols. In at least one embodiment, the diol is chosen
from: ethylene glycol, diethylene glycol, triethylene glycol,
1,3-propanediol, cyclohexanedimethanol and 4-butanediol. Other
polyols that may be used include glycerol, pentaerythritol,
sorbitol and trimethylolpropane.
[0236] The polyesteramides may be obtained in a manner analogous to
that of the polyesters, by polycondensation of diacids with
diamines or amino alcohols. Diamines that may be used are
ethylenediamine, hexamethylenediamine and meta- or
para-phenylenediamine. An amino alcohol that may be used is
monoethanolamine.
[0237] The polyester may also comprise at least one monomer bearing
at least one group --SO.sub.3M, wherein M is chosen from a hydrogen
atom, an ammonium ion NH.sub.4.sup.+ and a metal ion such as, for
example, an Na.sup.+, Li.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+,
Cu.sup.2+, Fe.sup.2+ or Fe.sup.3+ ion. A difunctional aromatic
monomer comprising such a group --SO.sub.3M may be used in at least
one embodiment.
[0238] The aromatic nucleus of the difunctional aromatic monomer
also bearing a group --SO.sub.3M as described above may be chosen,
for example, from benzene, naphthalene, anthracene, biphenyl,
oxybiphenyl, sulfonylbiphenyl and methylenebiphenyl nuclei. As
examples of difunctional aromatic monomers also bearing a group
--SO.sub.3M, non-limiting mention may be made of: sulfoisophthalic
acid, sulfoterephthalic acid, sulfophthalic acid,
4-sulfonaphthalene-2,7-dicarboxylic acid.
[0239] The copolymers used in at least one embodiment are those
based on isophthalate/sulfoisophthalate, and, for example,
copolymers obtained by condensation of diethylene glycol,
cyclohexanedimethanol, isophthalic acid and sulfoisophthalic
acid.
[0240] The polymers of natural origin, optionally modified, may be
chosen from shellac resin, sandarac gum, dammar resins, elemi gums,
copal resins and cellulose polymers, and mixtures thereof.
[0241] According to at least one embodiment of the composition
according to the present disclosure, the film-forming polymer may
be a water-soluble polymer and may be present in an aqueous phase
of the composition; the polymer is thus solubilized in the aqueous
phase of the composition.
[0242] According to at least one other embodiment of the
composition according to the present disclosure, the film-forming
polymer may be a polymer dissolved in a liquid fatty phase
comprising organic solvents or oils such as those described above
(the film-forming polymer is then said to be a liposoluble
polymer).
[0243] In at least one embodiment, the liquid fatty phase comprises
a volatile oil, optionally mixed with a non-volatile oil, the oils
being chosen from, for example, those mentioned above.
[0244] Non-limiting examples of liposoluble polymers which may be
mentioned include copolymers of vinyl ester (the vinyl group being
directly linked to the oxygen atom of the ester group and the vinyl
ester containing a saturated, linear or branched hydrocarbon-based
radical of 1 to 19 carbon atoms, linked to the carbonyl of the
ester group) and of at least one other monomer which may be a vinyl
ester (other than the vinyl ester already present), an
.alpha.-olefin (containing from 8 to 28 carbon atoms), an alkyl
vinyl ether (wherein the alkyl group comprises from 2 to 18 carbon
atoms) or an allylic or methallylic ester (containing a saturated,
linear or branched hydrocarbon-based radical of 1 to 19 carbon
atoms, linked to the carbonyl of the ester group).
[0245] These copolymers may be crosslinked with the aid of
crosslinking agents, which may be either of the vinyl type or of
the allylic or methallylic type, such as tetraallyloxyethane,
divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and
divinyl octadecanedioate.
[0246] Non-limiting examples of these copolymers that may be
mentioned include the following copolymers: vinyl acetate/allyl
stearate, vinyl acetate/vinyl laurate, vinyl acetate/vinyl
stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl
ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl
laurate, vinyl stearate/1-octadecene, vinyl acetate/1-dodecene,
vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl
ether, vinyl stearate/allyl acetate, vinyl
2,2-dimethyloctanoate/vinyl laurate, allyl
2,2-dimethylpentanoate/vinyl laurate, vinyl
dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl
stearate, vinyl propionate/vinyl stearate, crosslinked with 0.2%
divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked
with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether,
crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl
stearate, crosslinked with 0.2% divinylbenzene, vinyl
acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and
allyl propionate/allyl stearate, crosslinked with 0.2%
divinylbenzene.
[0247] Non-limiting examples of liposoluble film-forming polymers
which may also be mentioned include liposoluble copolymers, such as
those resulting from the copolymerization of vinyl esters
containing from 9 to 22 carbon atoms or of alkyl acrylates or
methacrylates, and alkyl radicals containing from 10 to 20 carbon
atoms.
[0248] Such liposoluble copolymers may be chosen from polyvinyl
stearate, polyvinyl stearate crosslinked with the aid of
divinylbenzene, of diallyl ether or of diallyl phthalate,
polystearyl (meth)acrylate, polyvinyl laurate and polylauryl
(meth)acrylate, it being possible for these poly(meth)acrylates to
be crosslinked with the aid of ethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate.
[0249] The liposoluble copolymers defined above are known and are
described, for example, in French Patent Application No. FR-A-2 232
303. In at least one embodiment, they may have a weight-average
molecular weight ranging from 2000 to 500,000, such as, for
example, from 4000 to 200,000.
[0250] As liposoluble film-forming polymers which may be used in
the present disclosure, non-limiting mention may also be made of
polyalkylenes, for example copolymers of C.sub.2-C.sub.20 alkenes,
such as polybutene, alkylcelluloses with a linear or branched,
saturated or unsaturated C.sub.1-C.sub.8 alkyl radical, for
instance ethylcellulose and propylcellulose, copolymers of
vinylpyrrolidone (VP) and, for example, copolymers of
vinylpyrrolidone and of C.sub.2 to C.sub.40 or C.sub.3 to C.sub.20
alkenes. As examples of VP copolymers which may be used in the
present disclosure, non-limiting mention may be made of the
copolymers of VP/vinyl acetate, VP/ethyl methacrylate, butylated
polyvinylpyrrolidone (PVP), VP/ethyl methacrylate/methacrylic acid,
VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene or
VP/acrylic acid/lauryl methacrylate.
[0251] Non-limiting mention may also be made of silicone resins,
which can be soluble or swellable in silicone oils, which are
crosslinked polyorganosiloxane polymers. The nomenclature of
silicone resins is known under the name "MDTQ," with the resin
being described as a function of the various siloxane monomer units
it comprises, each of the letters "MDTQ" characterizing a type of
unit.
[0252] Non-limiting examples of commercially available
polymethylsilsesquioxane resins that may be mentioned include those
sold:
[0253] by the company Wacker under the reference RESIN MK, such as
BELSIL PMS MK; and
[0254] by the company Shin-Etsu under the reference KR-220L.
[0255] Siloxysilicate resins that may be used according to at least
one embodiment, include trimethyl siloxysilicate (TMS) resins such
as those sold under the reference SR 1000 by the company General
Electric or under the reference TMS 803 by the company Wacker.
Non-limiting mention may also be made of the trimethyl
siloxysilicate resins sold in a solvent such as cyclomethicone,
sold under the name KF-7312J by the company Shin-Etsu, and DC 749
and DC 593 by the company Dow Corning.
[0256] Non-limiting mention may also be made of silicone resin
copolymers such as those mentioned above with
polydimethylsiloxanes, for instance the pressure-sensitive adhesive
copolymers sold by the company Dow Corning under the reference
Bio-PSA and described in U.S. Pat. No. 5,162,410, or the silicone
copolymers derived from the reaction of a silicone resin, such as
those described above, and of a diorganosiloxane, as described in
International Patent Application No. WO 2004/073626.
[0257] According to at least one embodiment of the present
disclosure, the film-forming polymer is a film-forming linear block
ethylenic polymer, which may comprise at least one first block and
at least one second block with different glass transition
temperatures (Tg), the at least one first and second blocks being
linked together via an intermediate block comprising at least one
constituent monomer of the first block and at least one constituent
monomer of the second block.
[0258] In at least one embodiment, the at least one first and
second blocks of the block polymer are mutually incompatible.
[0259] Such polymers are described, for example, in European Patent
No. EP 1 411 069 or International Patent Application No. WO
04/028488.
[0260] The film-forming polymer may also be present in the
composition in the form of particles dispersed in an aqueous phase
or in a non-aqueous solvent phase, which is generally known as a
latex or pseudolatex. The techniques for preparing these
dispersions are well known to those skilled in the art.
[0261] Non-limiting examples of aqueous dispersions of film-forming
polymers that may be used include the acrylic dispersions sold
under the names Neocryl XK-90.RTM., Neocryl A-1070.RTM., Neocryl
A-1090.RTM., Neocryl BT-62.RTM., Neocryl A-1079.RTM. and Neocryl
A-523.RTM. by the company Avecia-Neoresins, Dow Latex 432.RTM. by
the company Dow Chemical, Daitosol 5000 AD.RTM. or Daitosol 5000
SJ.RTM. by the company Daito Kasey Kogyo; Syntran 5760.RTM. by the
company Interpolymer, Allianz OPT by the company Rohm & Haas,
aqueous dispersions of acrylic or styrene/acrylic polymers sold
under the brand name Joncryl.RTM. by the company Johnson Polymer,
or the aqueous dispersions of polyurethane sold under the names
Neorez R-981.RTM.and Neorez R-974.RTM. by the company
Avecia-Neoresins, Avalure UR-405.RTM., Avalure UR-410.RTM., Avalure
UR-425.RTM., Avalure UR-450.RTM., Sancure 875.RTM., Sancure
861.RTM., Sancure 878.RTM. and Sancure 2060.RTM. by the company
Goodrich, Impranil 85.RTM. by the company Bayer and Aquamere
H-1511.RTM. by the company Hydromer; the sulfopolyesters sold under
the brand name Eastman AQ.RTM. by the company Eastman Chemical
Products, and vinyl dispersions, for instance Mexomer PAM.RTM. from
the company Chimex, and mixtures thereof.
[0262] Non-limiting examples of non-aqueous film-forming polymer
dispersions that may also be mentioned include acrylic dispersions
in isododecane, for instance Mexomer PAP.RTM. from the company
Chimex, and dispersions of particles of a grafted ethylenic
polymer, such as an acrylic polymer, in a liquid fatty phase, the
ethylenic polymer, for example, being dispersed in the absence of
additional stabilizer at the surface of the particles as described
in International Patent Application No. WO 04/055081.
[0263] The composition according to at least one embodiment of the
present disclosure may comprise a plasticizer that promotes the
formation of a film with the film-forming polymer. Such a
plasticizer may be chosen from any compound known to those skilled
in the art as being capable of fulfilling the desired function.
Dyestuff
[0264] In at least one embodiment of the present disclosure, the
composition may also comprise at least one dyestuff, for instance
pulverulent dyes, liposoluble dyes and water-soluble dyes.
[0265] Pulverulent dyestuffs may be chosen from pigments and
nacres.
[0266] The pigments may be white or colored, mineral and/or
organic, and coated or uncoated. Among the mineral pigments that
may be used according to at least one embodiment, non-limiting
mention may be made of titanium dioxide, optionally
surface-treated, zirconium oxide, zinc oxide or cerium oxide, and
also iron oxide or chromium oxide, manganese violet, ultramarine
blue, chromium hydrate and ferric blue. Among non-limiting examples
of organic pigments that may used according to the present
disclosure, non-limiting mention may be made of carbon black,
pigments of D&C type, and lakes based on cochineal carmine or
on barium, strontium, calcium or aluminum.
[0267] The nacres may be chosen from white nacreous pigments such
as mica coated with titanium or with bismuth oxychloride, colored
nacreous pigments such as titanium mica with iron oxides, titanium
mica with, for example, ferric blue or chromium oxide, titanium
mica with an organic pigment of the abovementioned type, and also
nacreous pigments based on bismuth oxychloride.
[0268] The liposoluble dyes may be chosen from, for example, Sudan
Red, D&C Red 17, D&C Green 6, .beta.-carotene, soybean oil,
Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5,
quinoline yellow and annatto.
[0269] In at least one embodiment, these dyestuffs may be present
in an amount ranging from 0.01% to 30% by weight relative to the
total weight of the composition.
Fillers
[0270] According to at least one embodiment, the composition
according to the present disclosure may also comprise at least one
filler.
[0271] The fillers may be chosen from those that are well known to
those skilled in the art and commonly used in cosmetic
compositions. The fillers may be mineral or organic, and lamellar
or spherical. Non-limiting mention may be made of talc, mica,
silica, kaolin, polyamide powders, for instance the Nylon.RTM. sold
under the trade name Orgasol.RTM. by the company Atochem,
poly-.beta.-alanine powders and polyethylene powders, powders of
tetrafluoroethylene polymers, for instance Teflon.RTM.,
lauroyllysine, starch, boron nitride, expanded polymeric hollow
microspheres such as those of polyvinylidene
chloride/acrylonitrile, for instance the products sold under the
name Expancel.RTM. by the company Nobel Industrie, acrylic powders,
such as those sold under the name Polytrap.RTM. by the company Dow
Corning, polymethyl methacrylate particles and silicone resin
microbeads (for example Tospearls.RTM. from Toshiba), precipitated
calcium carbonate, magnesium carbonate and magnesium
hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica
Beads.RTM. from Maprecos), glass or ceramic microcapsules, metal
soaps derived from organic carboxylic acids containing from 8 to 22
carbon atoms, such as from 12 to 18 carbon atoms, for example zinc,
magnesium or lithium stearate, zinc laurate and magnesium
myristate.
[0272] In at least one embodiment a compound may be used that is
capable of swelling on heating, including heat-expandable particles
such as non-expanded microspheres of copolymer of vinylidene
chloride/acrylonitrile/methyl methacrylate or of acrylonitrile
homopolymer copolymer, for instance those sold, respectively, under
the references Expancel.RTM. 820 DU 40 and Expancel.RTM. 007WU by
the company Akzo Nobel.
[0273] In at least one embodiment, the fillers may be present in an
amount ranging from 0.1% to 25% by weight, such as, for example,
from 1% to 20% by weight, relative to the total weight of the
composition.
[0274] The coloring agent or the filler may also be present in the
form of a "particulate paste."
[0275] When it contains particles that are solid at room
temperature, the composition according to the disclosure can be
prepared by introducing them into the composition in the form of a
colloidal dispersion, also known as a "particulate paste," as
described in International Patent Application No. WO 02/39961, the
content of which is incorporated herein by reference.
[0276] For the purposes of the present disclosure, the expressions
"colloidal dispersion" and "particulate paste" mean a concentrated
colloidal dispersion of coated or uncoated particles in a
continuous medium that are stabilized using a dispersant or
optionally without a dispersant. These particles may be chosen from
pigments, nacres and solid fillers, and mixtures thereof. These
particles may be in any form, such as, for example, spherical or
elongated form like fibers. They are insoluble in the medium.
[0277] The dispersant serves to protect the dispersed particles
against their aggregation or flocculation. In at least one
embodiment, the dispersant used to stabilize a colloidal dispersion
is present in an amount ranging from 0.3 to 5 mg/m.sup.2, such as,
for example, from 0.5 to 4 mg/m.sup.2, of surface area of
particles. This dispersant may be a surfactant, an oligomer, a
polymer or a mixture of several of them, bearing at least one
functionality having a strong affinity for the surface of the
particles to be dispersed. For example, they may attach physically
or chemically to the surface of the pigments. These dispersants may
also contain at least one functional group that is compatible with
or soluble in the continuous medium. In at least one embodiment,
esters of 12-hydroxystearic acid and of a C.sub.8 to C.sub.20 fatty
acid and of a polyol, for instance glycerol or diglycerol, are
used, such as the stearate of poly(12-hydroxystearic acid) with a
molecular weight of about 750 g/mol, such as the product sold under
the name SOLSPERSE 21 000 by the company Avecia, the polyglyceryl-2
dipolyhydroxystearate (CTFA name) sold under the reference DEHYMYLS
PGPH by the company Henkel or polyhydroxystearic acid, such as the
product sold under the reference ARLACEL P100 by the company
Uniqema, and mixtures thereof.
[0278] As other dispersants which may be used in the composition of
the present disclosure, non-limiting mention may be made of
quaternary ammonium derivatives of polycondensed fatty acids, for
instance SOLSPERSE 17 000 sold by the company Avecia, and mixtures
of polydimethylsiloxane/oxypropylene, such as those sold by the
company Dow Corning under the references DC2-5185 and DC2-5225
C.
[0279] In at least one embodiment, polydihydroxystearic acid and
the 12-hydroxystearic acid esters can be used for a
hydrocarbon-based or fluorinated medium, whereas the mixtures of
oxyethylenated/oxypropylenated dimethylsiloxane can be used for a
silicone medium.
[0280] The colloidal dispersion is a suspension of particles that
are, for example, micron-sized (<10 .mu.m) in a continuous
medium. In at least one embodiment, the volume fraction of
particles in a concentrated dispersion ranges from 20% to 40%, or,
for example, greater than 30%, which corresponds to a weight
content that may be up to 70% depending on the density of the
particles.
[0281] The particles dispersed in the medium may comprise mineral
or organic particles or mixtures thereof, such as those described
below.
[0282] The continuous medium of the paste may be of any nature and
may contain any solvent or liquid fatty substance and mixtures
thereof. In at least one embodiment, the liquid medium of the
particulate paste is one of the liquid fatty substances or oils
that can be used in the composition, thus forming part of the
liquid fatty phase.
[0283] According to at least one embodiment, the "particulate
paste" or colloidal dispersion is a "pigmentary paste" containing a
colloidal dispersion of coated or uncoated colored particles. These
colored particles can be pigments, nacres or a mixture of pigments
and/or nacres.
[0284] In at least one embodiment, the colloidal dispersion is
present in an amount ranging from 0.5% to 30% by weight, such as,
for example, from 2% to 20% or from 2% to 15% by weight, relative
to the total weight of the composition.
[0285] The composition of the disclosure may also comprise at least
one additive usually used in cosmetics, such as antioxidants,
preserving agents, fibers, fragrances, neutralizers, thickeners,
vitamins, moisturizers, screening agents and in particular
sunscreens, coalescers and plasticizers, and mixtures thereof.
[0286] Needless to say, a person skilled in the art will take care
to select the optional additional additives and/or the amount
thereof such that the advantageous properties of the composition
according to the disclosure are not, or are not substantially,
adversely affected by the envisaged addition of the optional at
least one additive.
[0287] The compositions according to the disclosure may be prepared
according to methods known to those skilled in the art.
[0288] The composition used in the process according to the
disclosure may be packaged, for example, in a packaging and
application device comprising: [0289] i) a support; [0290] ii) an
at least partially convex application surface arranged on one face
of the support, the application surface being formed from at least
part of the side surface of a stick of the composition; and [0291]
iii) a plurality of application members, for example in the form of
a teeth or hairs, arranged in at least one row extending from at
least one side of the application surface, and protruding relative
to the face of the support.
[0292] A preferred packaging device is shown in FIG. 1, which is
shown merely as a guide and does not in any way limit the
disclosure. FIG. 1 shows a profile view in perspective of one
embodiment of a device according to the present disclosure.
[0293] The device 1 comprises a handle member 2 on which is
retained a support 3 presenting the application member 4 which
extends along a longitudinal axis X. Device 1 comprises a
longitudinal wall 16.
[0294] Application member 4 is cylindrical and comprises the
composition in stick form. Application member 4 comprises an
application surface 6 that can be placed in contact with keratin
fibers without any portion of support 3 coming into contact with
the keratin fibers.
[0295] Application member 4 rests on one face of support 3 and is
retained thereon, for example, by fixing means such as a ring 23.
To protect application surface 6 and application member 4 between
uses, a removable closing cap (not shown) can be mounted around
support 3 and, for example, retained thereon. The application
member 4 may, as shown in FIG. 1, project beyond the axial end 24
of the support 3 so as to have an axial end 50 forming an extension
of application surface 6.
[0296] Support 3 comprises a row 5 of application members 9
projecting from a longitudinal side edge 8 and extending laterally
along application member 4, for example against the outer edge of
one part of application member 4. Application surface 6 is thus
accessible beyond the free ends 10 of application members 9 and
also in the spaces between application members 9.
[0297] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the specification and
attached claims are approximations that may vary depending upon the
desired properties sought to be obtained by the present disclosure.
At the very least, and not as an attempt to limit the application
of the doctrine of equivalents to the scope of the claims, each
numerical parameter should be construed in light of the number of
significant digits and ordinary rounding approaches.
[0298] Notwithstanding the numerical ranges and parameters setting
forth the broad scope of the invention as approximations, the
numerical values set forth in the specific examples are reported as
precisely as possible. Any numerical value, however, inherently
contains certain errors necessarily resulting from the standard
deviation found in its respective testing measurement.
[0299] The examples that follow are intended to illustrate the
invention without, however, being limiting in nature. Unless
otherwise indicated, the amounts are given in grams.
EXAMPLE 1
[0300] TABLE-US-00001 Sucrose acetate isobutyrate 5 (Eastman SAIB
sold by Eastman Chemical) Mixture of linear-chain fatty alcohol
(C30-C50) and of 2.5 C30-C50 hydrocarbons (80/20) (Performacol 550L
from New Phase Technologies) Polyethylene wax (Polyethylene Wax AC
617 from Honeywell) 10.5 Dispersion of poly(methyl
methacrylate/acrylic acid) 67.82 particles surface-stabilized in
isododecane with a polystyrene/copoly(ethylene-propylene) diblock
copolymer sold under the name Kraton G1701, at a polymer solids
content of 24.5% (Mexomer PAP from Chimex) Black iron oxide 5
Stearate of the oligomer 12-polyhydroxystearic acid 0.16 (Solsperse
21000 from Avecia) Hydrogenated isoparaffin (6-8 mol of
isobutylene) 9 (Parleam from Nippon Oil Fats)
Procedure
[0301] A pigmentary paste was prepared in the following manner: the
Solsperse 21000 was dissolved in the Parleam at about 80.degree. C.
over 10-15 minutes and the black iron oxide was then added with
stirring using a Rayneri blender for 15 minutes. The mixture was
ground using a ball mill for about 40 minutes.
[0302] The waxes were then melted with the sucrose acetate
isobutyrate, the above pigmentary paste and the polyisobutene at
110.degree. C. in a heating pan for about 45 minutes with stirring
using a Rayneri blender.
[0303] After homogenization of the mixture, it was cooled to
90.degree. C. and the dispersion of acrylate polymer particles in
the isododecane was then added with stirring. After homogenization
of the mixture, the fluid was poured into a silicone aluminum mold
at 42.degree. C. It was left to stand for 10 minutes, the surface
of the sticks was then scraped and the sticks were then placed in a
freezer at -28.degree. C. for 45 minutes. After recrystallization,
the sticks were removed from the molds and placed in suitable
packaging.
[0304] This mascara had a hardness, measured according to the
protocol indicated hereinabove, of 1814 Pa.
EXAMPLE 2
[0305] TABLE-US-00002 Beeswax 15 Polyethylene wax (Performalene 500
from NPT) 0.5 Polymethyl trifluoropropyl dimethylsiloxane (100 cSt)
8.4 from Shin-Etsu Sucrose acetate isobutyrate (Eastman SAIB sold
by Eastman 3 Chemical) Mixture of linear-chain fatty alcohol
(C30-C50) and 2.5 of C30-C50 hydrocarbons (80/20) (Performacol 550L
from New Phase Technologies) Phenyltrimethylsiloxytrisiloxane (20
cSt) (DC556 from 2.6 Dow Corning) Cyclopentadimethylsiloxane (DC
245 Fluid from Dow 58.5 Corning) Stearate of the oligomer
12-polyhydroxystearic acid 0.174 (Solsperse 21000 from Avecia)
Black iron oxide 5.22 Hydrogenated isoparaffin (6-8 mol of
isobutylene) 7.1 (Parleam from Nippon Oil Fat) Isododcane qs
100
Procedure
[0306] A pigmentary paste was prepared in the following manner: the
Soisperse 21000 was dissolved in the Parleam at about 80.degree. C.
over 10-15 minutes and the black iron oxide was then added with
stirring using a Rayneri blender for 15 minutes. The mixture was
ground using a ball mill for about 40 minutes.
[0307] The waxes were melted with the sucrose acetate isobutyrate,
the above pigmentary paste, the polyisobutene and the
phenyltrimethylsiloxytrisiloxane at 110.degree. C. in a heating pan
for about 45 minutes with stirring using a Rayneri blender.
[0308] After homogenization of the mixture, it was cooled to
90.degree. C. and the polymethyl trifluoropropyl dimethylsiloxane,
the cyclopentadimethylsiloxane and the isododecane were then added
with stirring using a Rayneri blender.
[0309] After homogenization of the mixture, the fluid was poured
into a silicone aluminum mold at 42.degree. C. It was left to stand
for 10 minutes, the surface of the sticks was then scraped and the
sticks were then placed in a freezer at -28.degree. C. for 45
minutes. After recrystallization, the sticks were removed from the
molds and placed in suitable packaging.
[0310] The mascara of Example 2 had a hardness, measured according
to the protocol indicated hereinabove, of 2177 Pa.
* * * * *