1. Use of a water-soluble comb-type copolymer, made up of: a) at least one anionic monomer having a polymerizable vinyl group and a carboxyl moiety, and b) at least one macro-monomer having the formula (I): R – (PO)m – (EO)n – R’ (I) wherein: m and n are integers other than zero and less than or equal to 150, PO and EO designate respectively propylene oxide and ethylene oxide and are arranged either randomly or in a regular pattern; R designates a polymerizable unsaturated group, R’ is hydrogen or an alkyl group having 1-4 carbon atoms; said copolymer has a molecular weight between 20,000 and 400,000 g/mol, to homogenize cosmetic compositions for makeup and/or for the care of keratinous material comprising a film-forming polymer and a coloring pigment and/or a pearlescent pigment.

2. Use according to claim 1, wherein the copolymer is made up of: a) at least one monomer of (meth)acrylic acid and b) at least one macro-monomer having the formula (I): R – (PO)m – (EO)n – R’ (I) wherein: m and n are integers other than zero and lower than 150, PO and EO designate respectively propylene oxide and ethylene oxide and are arranged either randomly or in a regular pattern; R designates a polymerizable unsaturated group, 34 R’ is hydrogen or an alkyl group having 1-4 carbon atoms; the molecular weight of said copolymer being between 20,000 g/mol and 250,000 g/mol.

3. Use according to claim 1 or 2, in which said coloring pigment is chosen from the group that includes iron oxides, chromium oxides, zirconium oxides, zinc or cerium oxides, manganese purple, blue ultramarine, carbon black, chromium hydrate, and iron blue.

4. Use according to any one of the previous claims, in which the copolymer is made up of, expressing the percentage by weight of each of its components: a) 5% to 30% of at least one monomer of (meth)acrylic acid; b) 70% to 95% at least one macromonomer having the formula (I); c) 0% to 20% of at least one monomer which is an ester of (meth)acrylic acid; where the sum of the percentages a), b), and c) is 100%.

5. Use according to any one of the previous claims, in which the copolymer is made up of, expressing the percentage by weight of each of its components: a) 5% to 15% of at least one monomer of (meth)acrylic acid; b) 85% to 95% at least one macromonomer having the formula (I); c) 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid; where the sum of the percentages a), b), and c) is 100%.

6. Use according to any of the previous claims, in which the comb-type (meth)acrylic copolymer has a molecular weight between 30,000 and 380,000 g/mol, for example between 30,000 g/mol and 150,000 g/mol.

7. Use according to any one of the previous claims, whereby said cosmetic composition comprises 3 to 25 wt% of coloring pigments and/or pearlescent pigments and 8 to 15 wt% of film-forming polymer.

8. Use according to any one of the previous claims, wherein m and n are between 10 and 90 in formula (I). 35

9. Cosmetic composition for makeup and/or for the care of keratinous material, comprising: a) from 1 to 30 wt.% of pearlescent and/or coloring pigment; b) from 0.1 to 30 wt.% of film-forming polymer; and c) from 0.05 to 8 wt.% of a comb-type water-soluble copolymer made up of: c1) at least one anionic monomer having a polymerizable vinyl group and a carboxyl moiety, and c2) at least one macro-monomer having the formula (I): R – (PO)m – (EO)n – R’ (I) wherein: m and n are integers other than zero and lower than 150; PO and EO designate respectively propylene oxide and ethylene oxide and are arranged either randomly or in a regular pattern; R designates a polymerizable unsaturated group, R’ is hydrogen or an alkyl group having 1-4 carbon atoms; the molecular weight of said copolymer being between 20,000 g/mol and 400,000 g/mol.

10. Cosmetic composition according to claim 9, comprising: a) from 1 to 30 wt.% of coloring mineral pigment; b) from 0.1 to 30 wt.% of film-forming polymer; and c) between 0.5 to 8 wt.% of comb-type (meth)acrylic copolymer made up of: c1) at least one monomer of (meth)acrylic acid and c2) at least one macro-monomer having the formula (I): R – (PO)m – (EO)n – R’ (I) wherein: m and n are integers other than zero and lower than 150; PO and EO designate respectively propylene oxide and ethylene oxide and are arranged either randomly or in a regular pattern; R designates a polymerizable unsaturated group, 36 R’ is hydrogen or an alkyl group having 1-4 carbon atoms; the molecular weight of said copolymer being between 20,000 g/mol and 250,000 g/mol.

11. Cosmetic composition according to any one of the claims 9 or 10, comprising 1 to 80wt.% of volatile or non-volatile wax or oil.

12. Cosmetic composition according to any one of the claims 9 to 11, comprising 2 to 5wt.% of said copolymer.

13. Cosmetic composition according to any one of the claims 9 to 12, comprising 0.1% to 15wt.% of an aqueous-phase thickening agent.

14. Cosmetic composition according to anyone of the claims 9 to 13, comprising 0.5% to 20wt.% of a film-forming polymer.

15. Cosmetic composition according to anyone of the claims 9 to 14, comprising at least one other additive chosen from a group consisting of reflective particles, surfactants or emulsifiers, emollients, humectants, hydrating agents, neutralizing, acidifying, or alkalizing agents, preservatives, fillers, antioxidants, perfumes, plasticizers, cosmetic active ingredients, and sunscreens.

FORM 2
THE PATENT ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION
COPOLYMERS IN COSMETIC COMPOSITIONS
2. APPLICANT(S)
a) Name : COATEX
b) Nationality : FRENCH Company
c) Address : 35, RUE AMPÈRE,
F-69730 GENAY,
FRANCE
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention
and the manner in which it is to be performed : -
2
FIELD OF THE INVENTION
This invention concerns the cosmetic technical area, specifically the area of cosmetic
compositions for coating keratinous fibers. More specifically, this invention concerns the use
of a specific copolymer to homogenize compositions that include coloring pigments and/or
pearlescent pigments and film-forming polymers, as well as the cosmetic compositions
containing said copolymer.
BACKGROUND OF THE INVENTION
The cosmetic compositions intended to coat keratinous fibers, whose purpose in generally
makeup and/or care, traditionally comprise coloring material such as mineral pigments, for
example. In addition, the cosmetic compositions intended to coat keratinous fibers and which
must be resistant to water, steam, humidity, sebum, and tears (mascara formulations, for
example) generally comprise a film-forming polymer.
The person skilled in the art tries to control the rheological, particle size distribution,
stability, and sensory parameters during the implementation, storage, and post-use of the
cosmetic compositions and, more specifically, of the compositions for coating keratinous
fibers that comprise mineral or organic fillers, notably mineral pigments. For this purpose,
they use dispersing additives or dispersing agents.
These dispersing agents are capable of dispersing the mineral pigments, for example metal
oxide pigments such as iron oxide, in the compositions that contain them. In fact, a dispersing
agent is typically used in order to prevent the flocculation of the particles and the ensuing loss
of the desired properties. In practice, a dispersing agent included in a cosmetic formulation
comprising metal pigments, leads to a viscosity lower than that of the same cosmetic
formulation that does not contain said dispersing agent. The dispersing power of an agent in a
formulation is thus measured by determining the viscosity. In addition, dispersing agents
make it possible to stabilize the particle size distribution and texture parameters of the
compositions. They make it possible to homogenize said compositions.
There are four broad categories of dispersing agents in cosmetic compositions: oils,
surfactants, natural dispersants, and polymeric-type dispersants.
Additives of the cosmetic oils type, for example esters, such as the poly(hydroxystearic)
acids, and some surfactants are commercially available for dispersing the iron oxides in
cosmetic formulations for keratinous material. Nevertheless, these additives have the
3
drawback of negatively impacting the sensory aspect of the compositions that include them;
their use in these compositions is, therefore, limited.
Among the dispersants of natural or biosourced origin, one can mention the use of
lignosulphonates and carbohydrates of the inulin type (Abstract of Paper, 244th ACS
National Meeting & Exposition, Philadelphia, August 19-23, 2012 Washington DC) and of
acyl-poly(aminoacid), of poly-glutamate (US 20120076840 and JP 2012001503), and of
poly(aspartic) acids. These natural dispersants have the drawback that they need to be
purified in order to attain the molecular weight desired for optimum effectiveness as
dispersing agents in cosmetic compositions.
A number of documents in the prior art discuss the dispersion of mineral filler pigments with
polymeric additives.
One can cite, among them, J. Cosmet. Sci., 50, 105-109, 1999, which concerns, in a general
way, the water-based nail polish additives and which describes, notably, the implementation
of water-soluble polymers as thickeners, stabilizers, and pigment dispersants. The
homopolymers of ethylene oxide, of acrylic acid, of methacrylic acid, of polyvinyl alcohol,
and of various cellulosic materials are examples of these additives.
One can also cite the article Tenside Surf. Det., 36, 1999, which discusses a technical area
different than that of this invention. This document describes the impact of polymeric and
non-polymeric materials on the dispersion of iron oxide particles in the water used in
industrial processes (for example in heat exchangers and distillation systems). The following
polymers are specifically mentioned: polymers of acrylic acid, methacrylic acid, maleic acid,
acrylamide, 2-acrylamido-2-methylpropane sulphonic acid, and copolymers of acrylic acid.
Patent WO 2009073384 describes the use of acrylic organosilylated copolymers. These
commercially available copolymers have a non-negligible impact on the sensory and
organoleptic properties of cosmetic formulations.
In addition, incompatibility problems are encountered in the cosmetic compositions which
contain coloring mineral pigments of the metal oxide type, such as iron oxides, and which
also comprise film-forming polymers and dispersing agents of the polymeric type. The
simultaneous presence of two types of polymers within the cosmetic composition can, in
some cases, lead to instability problems, such as dephasing or phase separation, bleeding,
release, and deposition or sedimentation. This incompatibility becomes more important as the
4
concentrations of pigments and/or film-forming polymers (also called agent or film-forming
additive) are increased in said cosmetic compositions.
DESCRIPTION OF THE INVENTION
An object of this invention is to propose a polymeric additive that is compatible with the
film-forming polymers used in the cosmetic compositions intended for coating water-resistant
keratinous fibers, including the cases in which these film-forming polymers are present in
high concentrations.
A further object of this invention is to propose a polymeric additive that makes it possible to
efficiently disperse pearlescent pigments and/or coloring pigments used in said compositions,
including when said pearlescent and/or pigments are present in high concentrations. A further
object of this invention is to propose a copolymer that makes it possible to homogenize the
cosmetic compositions that comprise film-forming polymers as well as over 1 % and up to 20
wt.% of pearlescent and/or coloring pigments, specifically metal oxides such as iron oxides.
A further object of this invention is to propose a copolymer that makes the preparation of the
cosmetic composition easier, for example by preventing caking and/or flocculation.
A further object of this invention is to propose a cosmetic composition intended to coat
keratinous fibers which is resistant to water and which displays excellent stability on storage.
The inventors realized, to their surprise, that all these objectives are met by using a combtype
copolymer with a specific chemical composition and molecular weight.
In fact, the use of such a copolymer makes it possible to solve the incompatibility problems
observed with film-forming polymers used in waterproof mascara-type cosmetic
compositions; this enables the person skilled in the art, when preparing the formulation of her
cosmetic composition, to solve problems such as, for example, caking, the formation of
irreversible heterogeneities, and the precipitation of pigments when the various ingredients
are added. Such a copolymer also makes it possible to homogenize the cosmetic
compositions.
Moreover, the use of such a copolymer makes it possible to obtain cosmetic compositions
that are more stable on storage, while maintaining the desired organoleptic properties.
This invention concerns the use of a water-soluble comb-type copolymer having a skeleton
(principal chain) and side branches of polyalkylene glycol to homogenize cosmetic
5
compositions that include a film-forming polymer and pearlescent and/or coloring pigments,
in particular metal oxides such as iron oxide(s).
More specifically, the water-soluble copolymer is such that it comprises:
- at least one anionic monomer having a polymerizable vinyl group and a carboxyl moiety,
such as (meth)acrylic acid;
- at least one monomer having a polymerizable unsaturated group, ethylene oxide (EO)
units, and propylene oxide (PO) units, those EO and PO units potentially being
randomly sequenced or regularly sequenced.
Moreover, the copolymer of the invention has a specific molecular weight between 20,000
and 400,000 g/mol, for example between 20,000 and 250,000 g/mol.
Thus, an object of this invention concerns the use of a copolymer made up of:
a) at least one anionic monomer having a polymerizable vinyl group and a carboxyl
moiety, such as (meth)acrylic acid, and
b) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- where: m and n are integers other than zero and lower than 150,
- PO and EO respectively designate propylene oxide and ethylene oxide and are
arranged in a random or alternating block,
- R designates a polymerizable unsaturated group,
- R’ is hydrogen or an alkyl group having 1, 2, 3, or 4 carbon atoms,
said copolymer having a molecular weight between 20,000 and 400,000 g/mol and
homogenizing a cosmetic composition for makeup and/or for the care of keratinous material
comprising a film-forming polymer and a pearlescent pigments and/or a coloring pigment.
Another object of this invention concerns a cosmetic composition for makeup and/or for the
care of keratinous material, comprising:
a) from 1 to 30 wt.% of pearlescent and/or coloring pigment;
b) from 0.1 to 30 wt.% of film-forming polymer; and
c) from 0.05 to 8 wt.% of comb-type copolymer formed of:
6
c1) at least one anionic monomer having a polymerizable vinyl group and a
carboxyl moiety, such as (meth)acrylic acid, and
c2) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
- m and n are two integers other than zero and lower than 150;
- PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
- R designates a polymerizable unsaturated group;
- R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
the molecular weight of said copolymer being between 20,000 g/mol and
400,000 g/mol.
Another object of this invention regards the use of a copolymer according to the invention to
provide storage stability, as defined above, to a cosmetic composition for makeup and/or care
of the keratinous material comprising a film-forming polymer and a pearlescent and/or
coloring pigment, notably when the pearlescent and/or coloring pigment is present in a
concentration between 1% and 30wt.% relative to the total weight of the composition, and/or
when the film-forming polymer is present in a concentration between 0.1% and 30wt.%
relative to the total weight of the composition.
DEFINITIONS
In the context of the present invention, the limits of the indicated ranges (wt.%, molecular
weight, etc.) are included in the range.
"Pearlescent and/or coloring pigment" refers broadly to pulverulent coloring matters. These
pulverulent coloring matters may be chosen from among pigments and pearlescent materials.
The pigments may be white or colored, mineral and/or organic, coated or uncoated. Examples
of mineral pigments include titanium dioxide, potentially surface-treated, zirconium oxides,
zinc oxides, and cerium oxides, as well as iron or chromium oxides, manganese purple,
ultramarine blue, chromium hydrate, and iron blue. Examples of organic pigments include
carbon black, type D & C pigments, and lacquers made from cochineal carmine, barium,
7
strontium, calcium, and aluminum. The pearlescent materials may be chosen from white
pearlescent pigments such as mica covered with titanium or bismuth oxychloride, colored
pearlescent pigments such as titanium mica with iron oxides, titanium mica particularly with
iron blue or chromium oxide, titanium mica with an organic pigment of the aforementioned
type as well as pearlescent pigments made from bismuth oxychloride.
In the context of the present invention, the term “coloring mineral pigment” means materials
of mineral origin or obtained by a synthetic process, possibly chemically modified, which,
once blended and coformulated in cosmetic compositions, make it possible to obtain cosmetic
products of different colors or shades. The coloring pigment of the invention can be a
synthetic mineral pigment.
In one embodiment of this invention, the coloring pigment is chosen from the group that
includes iron oxides, chromium oxides, zirconium oxides, zinc or cerium oxides, manganese
violet, blue ultramarine, chromium hydrate, carbon black, and iron blue.
In another embodiment of this invention, the coloring mineral pigment is an iron oxide or a
mixture of iron oxides. The iron oxides are commercially available or custom produced.
“Film-forming polymer” means a polymer capable, by itself or in the presence of coadditives,
of generating a continuous film which adheres to keratinous material. Preferably,
this film is cohesive and can be isolated, if necessary. Synthetic polymers in the form of
dispersions or emulsions of said polymers (in the form of a latex, for example) can be
mentioned among the film-forming polymers.
The following examples of film-forming polymers according to the invention can be
mentioned:
- polycondensates: polyurethanes, acrylic polyurethanes, polyvinylpyrrolidone
polyurethanes, polyesters, polyester polyurethanes, polyureas, and mixtures
thereof,
- polymers obtained by radical polymerization: acrylic and/or vinyl copolymers
obtained by (co)polymerization of mono-unsaturated monomers and/or
polyethylene monomers such as acrylics, methacrylics, acrylic esters, styrenes, and
vinyls, and mixtures thereof. Acrylic/silicone copolymers such as hybrid
copolymers can also be mentioned.
According to this invention, the film-forming polymers are distinct from the water-soluble
dispersant copolymers that are the object of this invention.
8
According to this invention, “stability on storage” refers to a composition that, when placed
in an oven at 45°C for three months remains in an identical (or substantially identical) form
as that obtained just after formulation. Specifically, the composition is said to be stable on
storage if it does not display any of the following instabilities: Dephasing, phase separation,
creaming, bleeding, release, deposit or sedimentation.
Another object of this invention regards the use of a copolymer according to the invention to
provide storage stability, as defined above, to a cosmetic composition for makeup and/or care
of keratinous materials comprising a film-forming polymer and a coloring mineral pigment,
and this, notably, when the coloring mineral pigment is present in a concentration between
1% and 30wt.% relative to the total weight of the composition, and/or when the film-forming
polymer is present in a concentration between 0.1% and 30wt.% relative to the total weight of
the composition.
"Keratinous materials" refers to eyelashes, eyebrows, and hairs and/or hair. It is also possible
to apply the inventive composition to the skin.
"Anionic monomers having a polymerizable vinyl group and a carboxyl moiety" are
negatively charged monomers in a basic aqueous solution. The anionic monomers having a
polymerizable vinyl group and a carboxyl moiety are, for example, chosen from among
acrylic acid and/or methacrylic acid.
According to one aspect of the present invention, the copolymet comprises "at least one
(meth)acrylic acid monomer". "At least one monomer of (meth)acrylic acid” means at least
one monomer of acrylic acid or at least one monomer of methacrylic acid. According to this
invention, the copolymer may comprise monomers of acrylic acid and/or monomers of
methacrylic acid. Therefore, the (meth)acrylic acid skeleton of the inventive copolymer can
be made up exclusively of acrylic acid, exclusively of methacrylic acid, or of a mixture of
acrylic acid and methacrylic acid.
DETAILED DESCRIPTION OF THE INVENTION
The state of dispersion of the pearlescent pigments and/or coloring mineral pigments,
especially those of the iron oxide(s) type, as well as the decreased viscosity of the cosmetic
formulations, are linked to the molecular weight, composition, and architecture of the
copolymers of the invention.
9
In particular, the copolymer of the invention has a specific molecular weight between 20,000
and 400,000 g/mol, for example between 20,000 and 250,000 g/mol. The best viscosity
values, and therefore the best effect on the homogeneity of the compositions, are in fact
obtained in cosmetic compositions comprising copolymers of molecular weight in the middle
of this range.
In the context of this invention, “molecular weight” means the weight-average molecular
weight or Mw. The molecular weight is determined by size exclusion chromatography (SEC),
also called gel permeation chromatography (GPC).
According to one embodiment of the present invention, the copolymer has a molecular
weight of between 20,000 g/mol and 350,000 g/mol, for example between 30,000 g/mol and
380,000 g/mol, or between 40,000 g/mol and 250,000 g/mol.
In another embodiment of this invention, the copolymer has a molecular weight between
50,000 g/mol and 110,000 g/mol.
In one embodiment of the present invention, the copolymer is such that the R in the
macromonomer of formula (I) is a methacrylate group, a methacrylurethane group, an
acrylate group, a vinyl group, a methallyl group, or an allyl group.
Said copolymer of the invention is obtained through known conventional free radical
copolymerization processes in solution, in direct or inverse dispersion, in bulk, in suspension
or precipitation in suitable solvents, in the presence of known initiators and transfer agents; or
else, it is obtained through controlled free radical polymerization processes such as the
method called Reversible Addition Fragmentation Transfer (RAFT), the method called Atom
Transfer Radical Polymerization (ATRP), the method called Nitroxide Mediated
Polymerization (NMP), or, finally, the method called Cobaloxime Mediated Free Radical
Polymerization.
In one embodiment of the present invention, the copolymer also comprises an ester of
(meth)acrylic acid, for example ethyl acrylate.
In one embodiment of the present invention, the copolymer is a (meth)acrylic copolymer and
is made up of (expressing the percentage by weight of each of its components):
a) 5% to 30% of at least one monomer of (meth)acrylic acid;
10
b) 70% to 95% at least one macromonomer having the formula (I);
c) 0% to 20% of at least one monomer which is an ester of (meth)acrylic acid;
where the sum of the percentages a), b), and c) is 100%.
In another embodiment of the present invention, the copolymer is a (meth)acrylic copolymer
and is made up of (expressing the percentage by weight of each of its components):
a) 5% to 15% of at least one monomer of (meth)acrylic acid;
b) 85% to 95% at least one macromonomer having the formula (I);
c) 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid;
where the sum of the percentages a), b), and c) is 100%.
In one embodiment of the present invention, the copolymer is such that m and n in formula
(I) are between 10 and 90.
According to the invention, said copolymer can be entirely or partially neutralized by one or
more neutralization agents having a monovalent or polyvalent cation. Said agents can be
chosen, for example, from the group consisting of ammonium hydroxide; calcium or
magnesium hydroxides or oxides; sodium, potassium, or lithium hydroxides; primary,
secondary, or tertiary aliphatic and/or cyclic amines, such as, for example stearylamine,
ethanolamines (mono, di, and triethanolamine), mono and diethylamine, cyclohexylamine,
methylcyclohexylamine, aminomethyl propanol, and morpholin.
The copolymer of the invention has a dispersing effect in cosmetic compositions containing
pearlescent pigments and/or coloring pigments such as metal oxides, even at high pigment
volume concentrations (PVC).
In an embodiment of this invention, the cosmetic composition of the invention has a pigment
volume concentration specifically between 15% and 50%.
The “pigment volume concentration” is defined by the following equation:
PVC (%) = 100 x Vc / (Vc+Vl)
where Vc represents the volume of the coloring pigments, and
11
Vl represents the dry volume of the film-forming polymer in the cosmetic
composition.
In one embodiment of the present invention, the cosmetic composition comprises 1 to
30 wt% of pearlescent and/or coloring pigment, e.g. 1 to 20 wt% or 1 to 10 wt% (the %
ranges are inclusive of the endpoints).
In another embodiment of the present invention, the cosmetic composition comprises 3 to 30
wt% of pearlescent and/or coloring pigment, e.g. 3 to 20 wt% or 3 to 10 wt%.
In another embodiment of the present invention, the cosmetic composition comprises 0.1 to
20 wt.% of a film-forming polymer, e.g. 0.1 to 10 wt%.
According to one embodiment of the present invention, the cosmetic composition for makeup
and/or for the care of keratinous material, comprises:
a) from 3 to 25 wt.% of pearlescent and/or coloring pigment;
b) from 8 to 15 wt.% of film-forming polymer; and
c) from 0.05 to 8 wt.% of comb-type copolymer formed of:
c1) at least one anionic monomer having a polymerizable vinyl group and a
carboxyl moiety, such as (meth)acrylic acid, and
c2) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
- m and n are two integers other than zero and lower than 150;
- PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
- R designates a polymerizable unsaturated group,
- R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
the molecular weight of said copolymer being between 20,000 g/mol and
400,000 g/mol.
The inventive cosmetic composition may appear in the form of an aqueous continuous phase
or in anhydrous form, or in the form of a water-in-oil or oil-in-water emulsion or a water-in12
oil or oil-in-water dispersion. It may be solid, liquid, or pasty. The inventive composition
may thereby comprise an aqueous phase that may be formed essentially of water.
According to one embodiment of the present invention, these cosmetic compositions are
formed of at least two phases, i.e. an aqueous phase and a non-aqueous phase, said phases
potentially themselves incorporating solid particles such as pearlescent and/or coloring
pigments. The copolymer according to the present invention is generally incorporated into the
aqueous phase of the cosmetic composition, but it may be incorporated into the non-aqueous
phase.
Thus, according to one embodiment of the present invention, the cosmetic composition
comprises, relative to the composition’s total weight:
a) 10% to 99.9wt.% of aqueous phase;
b) 0.1% to 90% based on the total weight of non-aqueous phase;
the sum a) + b) being equal to 100%.
In another embodiment of the present invention, the cosmetic composition comprises, relative
to the composition’s total weight:
a) 15% to 99.5wt.% of aqueous phase;
b) 0.5 % to 85 % based on the total weight of non-aqueous phase;
the sum a) + b) being equal to 100%.
In yet another embodiment of the present invention, the cosmetic composition comprises,
relative to the composition’s total weight:
a) 50% to 70wt.% of aqueous phase;
b) 30 % to 50 % based on the total weight of non-aqueous phase;
the sum a) + b) being equal to 100%.
The aqueous phase of the composition can be made up of a mixture of water and watermiscible
organic solvents (miscibility in water greater than 50 wt.% at 25°C). These solvents
are chosen, among for example:the lower mono-alcohols comprising 1-5 carbon atoms, such
as ethanol and isopropanol; the glycols comprising 2 to 8 carbon atoms such as propylene
13
glycol, ethylene glycol, 1,3-butylene glycol, and dipropylene glycol; the C3-C4 ketones; the
C2-C4 aldehydes; and the ethoxylated alcohols.
The non-aqueous phase (or fatty phase) of the cosmetic composition of the present invention
may comprise natural or synthetic components not miscible with water, which are liquid at
room temperature (25°C) and/or solid at room temperature; notably, they can be chosen from
the category that includes waxes, oils, pasty fatty substances, gums, and mixtures thereof.
"Wax" in the context of the present invention refers to a lipophilic compound that is solid at
room temperature (25°C), may or may not be deformable, can reversibly change between
solid and liquid state, with a melting point greater than or equal to 30°C that may reach as
high as 200°C and particularly up to 120°C. By bringing wax to liquid state (melting point), it
is possible to make it miscible to oils and to form a microscopically homogeneous mixture,
but when the mixture's temperature is lowered to room temperature, the wax is recrystallized
in the mixture's oils. In particular, waxes that comply with the invention may have a melting
point greater than or equal to 45°C, and in particular greater than or equal to 55°C.
"Oil" refers to a fatty substance that is liquid at room temperature (25°C). The oil may be
volatile or non-volatile. A volatile oil may evaporate when it comes in contact with the skin
or keratinous fiber in less than an hour, at room temperature and atmospheric pressure. A
non-volatile oil is an oil that remains on the skin or keratinous fiber at room temperature and
atmospheric pressure. for at least several hours. The oil may be chosen from among all
physiologically acceptable oils, and particular those that are cosmetically acceptable,
particularly mineral, animal, vegetable, and synthetic oils; in particular, hydrocarbon and/or
silicone and/or fluorinated volatile or non-volatile oils and mixtures thereof. More
specifically, a hydrocarbon oil refers to an oil principally comprising carbon and hydrogen
atoms, and potentially one or more groups chosen from among hydroxyl, ester, ether, and
carboxyl groups. Volatile oils and non-volatile oils are commercially available.
The inventive composition may comprise wax and/or volatile or non-volatile oils in a
concentration ranging from 1 to 80 wt% in relation to the total weight of the composition, e.g.
5 to 70 wt%, or 10 to 50 wt%, or 15 to 40 wt%.
14
In another embodiment of the present invention, the cosmetic composition comprises 0.05 to
5 wt% of said copolymer as-is, e.g. 0.1 to 5 wt% or 0.1 to 3 wt%.
The composition of the invention may further comprise any additive normally used in
cosmetics.
Moreover, the cosmetic composition of the invention may contain one or more of the
following ingredients:
- reflecting particles;
- surfactant or emulsifying agents or emulsifiers;
- emollients;
- humectants, hydrating agents;
- neutralizing, acidifying, or alkalizing agents;
- preservatives;
- fillers;
- antioxidants;
- perfumes;
- plasticizers;
- cosmetic active ingredients such as vitamins;
- sunscreens.
These additives may be present in the composition in a concentration of 0.01 to 30% of the
total weight of the composition.
For example, the composition may comprise at least one other structuring agent, chosen from
among thickening agents, lipophilic gelling agents normally used in cosmetics, and mixtures
thereof.
Lipophilic gelling agents normally used in cosmetics include mineral lipophilic gelling agents
such as clays or silicas, organic polymer lipophilic gelling agents such as fully or partially
cross-linked elastomer organopolysiloxanes, sequenced polystyrene/copoly(ethylenepropylene)
copolymers, polyamides, and mixtures thereof. As for the aqueous phase of the
composition, it may be thickened by a thickening agent. Aqueous-phase thickening agents
that may be used according to the invention include cellulosic thickeners, clays,
15
polysaccharides, acrylic polymers, associative polymers, and mixtures thereof. Hydrophilic
thickening agents particularly include AMPS/acrylamide copolymers of the SEPIGEL or
SIMULGEL type (SEPPIC).
In the inventive composition, the concentration of aqueous-phase thickening agent may range
from 0.1 to 15 wt%, in relation to the total weight of the composition, e.g. from 1% to 10
wt%, or e.g. 1 to 5 wt%.
The composition may also comprise surface-active agents which are non-ionic, anionic,
cationic, amphoteric or also surface-active emulsifiers.
The inventive composition may comprise an auxiliary film-forming agent encouraging the
formation of a film with the film-forming polymer. Such a film-forming agent may be chosen
from among the compounds known to the person skilled in the art to potentially fulfill the
desired function, and particularly from among plasticizers and coalescing agents.
The fillers may be chosen from among those well-known to the person skilled in the art and
commonly used in cosmetic compositions.
The inventive cosmetic composition for makeup and/or for the care of keratinous material
can take the form of a product for the eyelashes, of a product for the eyebrows, or of a
makeup product for hair or hairs, more specifically the form of a mascara. It can be in fluid,
solid, or two-phase form. It can take, for example, the form of a stick or the form of a soft
paste.
This cosmetic composition can be applied over (“top coat”) or under (“base coat”) the
makeup.
EXAMPLES
In each of the following examples, the molecular weight of the copolymers of the invention is
determined by size exclusion chromatography (SEC) or gel permeation chromatography
(GPC).
Such a technique implements a WATERSTM liquid chromatography instrument equipped
with two detectors. One of these detectors combines dynamic/static light scattering at a 90°
angle with the measurement of the viscosity performed with a VISCOTEKTM MALVERNTM
viscometer. The other detector is a WATERSTM refractometric concentration detector.
16
This liquid chromatography instrumentation is equipped with size exclusion columns,
suitably chosen by the person skilled in the art to separate the polymers under study on the
basis of on their molecular weights. The liquid eluent is an aqueous solution containing 1% of
KNO3.
In detail, in a first stage, the polymerization solution is diluted to 0.9% based on dry weight in
the SEC eluent, which is a 1% solution of KNO3. It is then filtered on a
0.2 μm filter. 100 μL are then injected into the chromatograph (eluent: a 1% solution of
KNO3).
The liquid chromatograph contains an isocratic pump (WATERS 515) whose flow rate is set
to 0.8 mL/min. The chromatographic instrument also includes a furnace, which, in turn,
comprises the following system of columns in series: a GUARD COLUMN
ULTRAHYDROGEL WATERSTM precolumn 6 cm long with an interior diameter of
40 mm, an ULTRAHYDROGEL WATERSTM linear column 30 cm long with an interior
diameter of 7.8 mm, and two ULTRAHYDROGEL 120 ANGSTROM WATERSTM columns
30 cm long with an interior diameter of 7.8 mm. The detection system, meanwhile, is made
up of an RI WATERSTM 410 refractometric detector, and a
270 DUAL DETECTOR MALVERNTM dual detector including a viscometer and 90° light
scattering. The temperature of the furnace is brought to 55°C, and that of the refractometer to
45°C.
The chromatography instrument is calibrated with a single PEO 19k standard of the type
PolyCALTM MALVERNTM.
Example 1
The copolymers of the present invention are prepared according the methods described
below.
Test 1-1
In a 1-liter reactor with mechanical agitation and oil-bath heating, the following were
weighed out:
- 514 g of water;
- 27 g of methacrylic acid;
17
- 217 g of a macromonomer that is a poly(alkylene glycol) methacrylate with molecular
weight 3000 and formed of 70 wt% poly(ethylene oxide) and 30 wt% poly(propylene oxide)
and
- 23 g of water.
In a first container, 1 g of 1,8-dimercapto-3,6-dioxaoctane (DMDO) is weighed out.
In a second container, 1.54 g of ammonium persulfate and 5 g of deionized water are weighed
out.
The contents of container 1, then 2, are heated to 65°C in succession and at once.
The mixture is then baked for 3 hours at 65°C.
The mixture is then neutralized with 50% sodium hydroxide to a pH of 7 and diluted to a
concentration of 25% dry material.
The final polymer has the following characteristic: Mw = 350,000 g/mol.
Test 1-2
In a 1-liter reactor with mechanical agitation and oil-bath heating, 284 g of water was
weighed out:
In a first container, the following are weighed out:
- 48.7 g of methacrylic acid;
- 339.5 g of a macromonomer that is a poly(alkylene glycol) methacrylate with molecular
weight 3,000 and formed of 70 wt% poly(ethylene oxide) and 30 wt% poly(propylene oxide)
and
- 25.4 g of water.
In a second container, 2.44 g of 1,8-dimercapto-3,6-dioxaoctane (DMDO) is weighed out.
In a third container, a solution of 1.44 g of ammonium persulfate and 80 g of deionized water
is weighed out.
The three ingredients from the three containers are brought to 65°C for three hours in the
heated, agitated reactor.
They are then baked for an additional hour at 67°C.
The mixture is then neutralized with 50% sodium hydroxide to a pH of 7 and diluted to a
concentration of 40 % dry material.
The final polymer has the following characteristic: Mw = 71,000 g/mol.
18
Test 1-3
In a 1-liter reactor with mechanical agitation and oil-bath heating, 257 g of water was
weighed out:
In a first container, the following are weighed out:
- 50.0 g of acrylic acid;
- 339.5 g of a macromonomer that is a poly(alkylene glycol) methacrylate with molecular
weight 3,000 and formed of 70 wt% poly(ethylene oxide) and 30 wt% poly(propylene oxide)
and
- 21 g of water.
In a second container, 4.45 g of 1,8-dimercapto-3,6-dioxaoctane (DMDO) is weighed out.
In a third container, a solution of 3.6 g of ammonium persulfate and 80 g of deionized water
is prepared.
The ingredients from the three containers are brought to 65°C for three hours in the heated,
agitated reactor.They are then baked for an additional hour at 67°C.
The mixture is then neutralized with 50% sodium hydroxide to a pH of 7 and diluted to a
concentration of 40 % dry material.
The final polymer has the following characteristic: Mw = 45,000 g/mol.
All of the examples 1 to 5 that follow illustrate the use of copolymers according to tests 1-1
to 1-3 in various mascara composition formulations. The figures listed in the last column of
the table indicate the weights in grams.
The results (not shown) also indicate that selecting the macromonomer together with the
copolymer’s molecular weight leads to homogeneous compositions characterized by a
decrease in viscosity that do not exhibit any problems (generating heterogeneities,
precipitation, depletion, etc.) during the preparation of the mascara and which are stable on
storage. It can therefore be deduced that there is a good level of compatibility between the
polymer of the invention and the film-forming polymer used in a cosmetic formulation that
comprises different black iron oxides or organic pigments.
19
Example 2
Table 1
The compounds of phase B are melted at 98°C then homogenized during agitation. Black iron
oxide is dispersed in water in the presence of other compounds of phase A. The homogeneous
phase A is then heated during moderated agitation to 93°C, then incorporated during heavy
agitation into phase B. The mixture is mixed for 5 minutes, then its temperature is lowered to
40°C. Phase C is then incorporated during moderate agitation.
The tests are then cooled to room temperature during moderate agitation, then added to
flasks.
A sample of clean, homogeneously colored blond hair is divided in two to conduct mascara
tests.
The tests are used to carefully coat the hair. After being coated, the hair is dried using a hair
dryer at 65°C. The coloring of the hair samples resulting from the two tests is measured using
a surface colorimeter. From the L.a.b measurement, the value L is used to determine the color
intensity of each test. The test with the polymer of the invention (example 2-2) shows a color
intensity 9 % more than the test of the prior art (example 2-1).
2-1 2-2
Prior art Invention
Phase A
Deionized water q.s.f. 100 q.s.f. 100
Black iron oxide (BK 5000 HP – Mineral and Pigment Solutions Inc.) 7 7
Polymer Test 1-1 (quantity as-is) 0 0.1
Preservative 0.1 0.1
Antifoaming agent 0.1 0.1
PEG-200 Glyceryl stearate (Simulsol 220 - Seppic) 4 4
Phase B
Beeswax 7.4 7.4
Carnauba wax 3.5 3.5
Phase C
Copolymer of acrylamide and sodium acrylamido-2-methylpropane
sulfonate in an inverse emulsion in isohexadecane (Simulgel 600 -
Seppic)
3.5 3.5
Aqueous dispersion of polyurethane (polycaprolactone/4,4' diphenyl
methane diisocyanate) (Disperbond D31W40 - Merquinsa) – Filmforming
polymer
8 8
20
Example 3
3-1 3-2
Prior art Invention
Phase A
Deionized water q.s.f. 100 q.s.f. 100
Red iron oxide (CG160 - Mineral and Pigment Solutions Inc.) 6 6
Polymer Test 1-2 (quantity as-is) 0 0.1
Preservative 0.1 0.1
Ethanol 10 10
Propylene glycol 2 2
Phase B
Deionized water 30 30
Polyvinyl alcohol (Selvol PVA 125 - Sekisui) 1 1
Gum arabic 3 3
Hydroxyethyl cellulose (Cellosize HEC QP 300 - Amerchol) 1.5 1.5
Sodium polystyrene sulfonate (Flexan II - Akzo Nobel) 1 1
Copolymer of styrene and acrylate (Joncryl 77 - BASF) – film-forming
polymer 10 10
Phase C
Deionized water 11.25 11.25
Carnauba wax 5.4 5.4
PEG-30 Glyceryl Stearate (Tagat S - Goldschmidt) 1.35 1.35
Ethanol 2 2
Table 2
The PVA, gum arabic, and hydroxyethyl cellulose are dispersed and then dissolved in the
water of phase B.
After dissolution, the other compounds of phase B are added and mixed.
The wax and surfactant of phase C are heated to 90°C, then homogenized.
The water of phase C, previously heated to 90°C, is then incorporated into the wax and
surfactant mixture, then the whole solution is carefully mixed for 10 minutes, after which the
mixture is cooled to 40°C, then the ethanol is added, and after mixing, phase C is cooled to
room temperature.
The compounds of phase A are mixed to disperse the red iron oxide.
Phase C and then phase B are added during agitation to the phase A created in this way.
The mixture is homogenized for 10 minutes, then added to a flask.
21
A sample of clean, homogeneously colored blond hair is divided in two to conduct mascara
tests.
The tests are used to carefully coat the hair.
After being coated, the hair is dried using a hair dryer at 40°C.
The coloring of the hair samples resulting from the two tests is measured using a surface
colorimeter.
From the L.a.b measurement, the value L is used to determine the color intensity of each test.
The test with the polymer of the invention (example 3-2) shows a color intensity 12% more
than the test of the prior art (example 3-1).
Example 4
4-1 4-2
Prior art Invention
Phase A
Deionized water 5 5
Black iron oxide (BK 5000 HP – Mineral and Pigment Solutions
Inc.) 3 3
Yellow iron oxide (PURICOLOR Yellow PYE42 – BASF) 1 1
Polymer Test 1-2 (quantity as-is) 0 0.1
Preservative 0.1 0.1
Propylene carbonate 2 2
Phase B
Paraffin wax 2.5 2.5
Carnauba wax 6 6
Beeswax 5 5
C20-C40 alkyl (hydroxystearyloxy)stearate (Kester Wax K82P -
Koster Keunen) 3.5 3.5
Polyethylene wax 2 2
Vinyl polylaurate (Mexomère PP - Chimex) 0.75 0.75
Copolymer of vinyl acetate/allyl stearate (Mexomère PQ - Chimex)
– Film-forming polymer 2.2 2.2
Modified hectorite (Bentone 27V - Elementis) 5.5 5.5
Phase C
Isododecane q.s.f. 100 q.s.f. 100
Table 3
22
The compounds of phase B are melted at 98°C then homogenized during agitation. Black and
yellow iron oxides are dispersed in water in the presence of other compounds of phase A. The
homogeneous phase A is then heated during moderated agitation to 93°C, then incorporated
during heavy agitation into phase B. The mixture is mixed for 5 minutes, then its temperature
is lowered to 70°C. Phase C is then incorporated during moderate agitation. The tests are then
cooled to room temperature during moderate agitation, then added to flasks.
A sample of clean, homogeneously colored blond hair is divided in two to conduct mascara
tests.
The tests are used to carefully coat the hair. After being coated, the hair is dried using a hair
dryer at 65°C. The coloring of the hair samples resulting from the two tests is measured using
a surface colorimeter. From the L.a.b measurement, the value L is used to determine the color
intensity of each test. The test with the polymer of the invention (example 4-2) shows a color
intensity 14 % more than the test of the prior art (example 4-1).
Example 5
5-1 5-2
Prior art Invention
Phase A
Deionized water q.s.f. 100 q.s.f. 100
Green organic pigment (Vibracolor Green PGR7 - BASF) 0.5 0.5
Blue organic pigment (Vibracolor Blue PBL 15:3-L - BASF) 4.5 4.5
Polymer Test 1-3 (quantity as-is) 0 0.1
Preservative 0.1 0.1
Simethicone (antifoaming agent) 0.4 0.4
Phase B
Candelilla wax - Binder 24 24
Vinylpyrrolidone Copolymer - Eicosene (Ganex V220 - Ashland) –
film-forming polymer 1 1
Secondary alkyl sulfonate C14-C17 (Hostapur SAS - Clariant) 5 5
Phase C
Hydroxyethyl cellulose (Cellosize HEC QP 300 - Amerchol) 0.9 0.9
Table 4
The Candelilla wax of phase B is melted to 80°C, then the copolymer of VP-Eicosene and
Hostapur SAS 60 is added and mixed during agitation. The blue and green organic pigments
are dispersed in water in the presence of other compounds of phase A. The homogeneous
phase A is then heated during moderated agitation to 75°C, then incorporated during heavy
23
agitation into phase B. The mixture is mixed for 5 minutes, then its temperature is lowered to
40°C. Phase C is then incorporated during moderate agitation. The tests are then cooled to
room temperature during moderate agitation, then added to flasks.
A sample of clean, homogeneously colored blond hair is divided in two to conduct mascara
tests.
The tests are used to carefully coat the hair. After being coated, the hair is dried using a hair
dryer at 65°C. The coloring of the hair samples resulting from the two tests is measured using
a surface colorimeter. From the L.a.b measurement, the value L is used to determine the color
intensity of each test. The test with the polymer of the invention (example 5-2) shows a color
intensity 17 % more than the test of the prior art (example 5-1).
Example 6
A mascara composition is prepared, using the ingredients listed in the table below. The
figures listed in the last column of the table indicate the weights in grams.
Table 5
A
A-1 Deionized Water q.s.f. 100
A-2 Methylparaben NF (Protameen) 0.10
A-3 Methocel 40-202 (Dow Chemical) 0.20
A-4 triethanolamine (99%) 2.80
A-5 DL Panthenol USP (DSM) 0.50
A-6 Avalure UR 450 (Lubrizol) 6.00
A-7 PVP K-30 (ISP) 2.00
A-8 Polymer additive as is 0 or 3.00
B B-8 Iron Oxide Black 34PC3068 (Emerald Hilton Davis) 10.00
C
C-9 Emersol 132 (Cognis) 5.50
C-10 Bayberry wax (F. B. Ross) 1.80
C-11 Protachem GMS 450 (Protameen) 1.70
C-12 Beeswax white (F. B. Ross) 4.50
C-13 Carnauba wax N°1 2.70
C-14 WW Gum Rosin (Akzo) 1.80
C-15 Propylparaben NF (Protameen) 0.10
D
D-16 Mirasil SM (Rhodia) 0.10
D-17 Lipovol WGO (Clariant) 0.10
D-18 Phenonip (Clariant) 0.10
D-19 Germaben II (ISP) 0.50
24
Phase A (aqueous phase):
A-1 is agitated and heated to 40°C, then A-2 is dissolved into A-1. The agitation is stopped,
then A-3 is added. Agitation continues until a homogeneous mixture is obtained. The
triethanolamine A-4 is added to the mixture. A-5 and then the film-forming polymer A-6
(6wt.%) are then incorporated under agitation. Finally, the film-forming polymer A-7
(2wt.%) and possibly a 40 % solution of the active material of the polymer A-8 (3wt.% of the
polymer as is, or 1.2 wt. % dry weight) are added. After complete homogenization is
achieved, the temperature is raised to 75°C.
Phases B (non-aqueous phase), C & D:
All ingredients of phase C are mixed at a temperature of 75°C. The coloring mineral pigment
B-8 (10wt.%) is incorporated. Mixing is continued and the temperature is lowered to 50°C.
The ingredients D-16, D-17, D-18, and D-19 are introduced, while still stirring.
Finally, the aqueous phase A is mixed with the blend of the phases B, C, and D. A
formulation of the type water-in-oil is therefore obtained.
Test 6-1
This test represents the standard; it does not implement any additional A-8 ingredient besides
those mentioned in the table.
Test 6-2
This test represents the prior art and implements, as A-8 ingredient, a polymer made up of
100% acrylic acid, entirely neutralized with sodium hydroxide, and having a weight-averaged
molecular weight of 4,500 g/mol.
The polymers of tests 6-3 to 6-7 are prepared according to a method similar to that of tests 1-
1 to 1-3 of example 1.
Test 6-3
This test represents the use of a polymer outside of the invention. It uses as A-8 ingredient, a
copolymer made up of each of its monomers in the respective percentages:
a) 8.14% of acrylic acid;
b) 2.79% of methacrylic acid; and
25
c) 89.07% of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 15, n = 46;
- PO and EO designate respectively propylene oxide and ethylene oxide;
- R designates the methacrylate group;
- R’ represents hydrogen;
completely neutralized with sodium hydroxide (NaOH), and having a molecular weight Mw
of 1,800,000 g/mol.
Test 6-4
This test represents the invention and implements a copolymer made up of each of its
monomers in the respective percentages by weight:
a) 7.5% of methacrylic acid; and
b) 92.5 % of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 15, n = 46;
- PO and EO designate respectively propylene oxide and ethylene oxide;
- R designates the methacrylate group;
- R’ represents hydrogen;
completely neutralized with sodium hydroxide, and having a molecular weight Mw of
120,000 g/mol.
Test 6-5
This test represents the invention and implements a copolymer made up of each of its
monomers in the respective percentages by weight:
a) 12.5% of methacrylic acid;
b) 87.5 % of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 15, n = 46;
- PO and EO designate respectively propylene oxide and ethylene oxide;
- R designates the methacrylate group;
- R’ represents hydrogen;
26
completely neutralized with sodium hydroxide, and having a molecular weight Mw of
75,000 g/mol.
Test 6-6
This test represents the invention and implements a copolymer made up of each of its
monomers in the respective percentages by weight:
a) 12.8% of acrylic acid;
b) 87.2 % of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 15, n = 46;
- PO and EO designate respectively propylene oxide and ethylene oxide;
- R designates the methacrylate group;
- R’ represents hydrogen;
completely neutralized with sodium hydroxide, and having a molecular weight Mw of
45,000 g/mol.
Test 6-7
This test represents the use of a polymer outside of the invention. It implements a copolymer
made up of each of its monomers in the respective percentages by weight:
a) 5.1% of acrylic acid and
b) 94.9 % of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 0, n = 113;
- EO designated ethylene oxide;
- R designates the methacrylate group;
- R’ designates the methyl radical;
completely neutralized with sodium hydroxide, and having a weight-averaged molecular
weight Mw of 65,000 g/mol.
Viscosity measurement
The viscosities are measured with a Brookfield model RVT viscometer. Each one of the
mascara formulations is contained in standard glass flasks. Each one of the formulations is
left to rest for 24 hours at 25°C before its viscosity is measured. The spindle must be centered
27
relative to the flask’s opening and is dipped until the surface of the formulation is flush with
the benchmark.
The viscosity is then measured at 20 rpm. The rotation is continued until the viscosity reading
is stable.
Preparation of mascaras and assessment of their organoleptic properties
Each formulation is prepared as described above. The organoleptic properties are observed at
room temperature. The following criteria are taken into account: Spread (coverage), Texture
(smooth, presence of lumps, granules, “custard like” or stringy appearance), Smell (whether a
smell develops or not), Color (change in the homogeneity of the color), Surface (smooth or
not).
Stability of mascaras on storage:
Each one of the mascara formulations is contained in a suitable 120 ml glass flask. The flasks
are then placed into an oven at 45°C.At time = 3 months, the flasks are removed from the
oven and the following potential instabilities are observed: dephasing or phase separation,
creaming, bleeding, release, deposition or sedimentation.
Test REFerence/PA/INVention/
Outside INvention
Brookfield
Viscosity
(cPs, 20 rpm,
25°C)
Preparation &
Organoleptic properties
Stability on
storage
Ageing for
3 months at
45°C
6-1 REF 14,610
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Beginning of
sedimentation
- Bleeding
6-2 PA
Not
measurable
* Preparation: unstable
Flocculation & Depletion
* Organoleptic: NA
Conclusion: Unstable
NA*
6-3 O-IN 14,050
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: grainy
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: slightly
unstable
Sedimentation
- release
28
Test
REFerence/PA/INVention/
Outside INvention
Brookfield
Viscosity
(cPs, 20 rpm,
25°C)
Preparation &
Organoleptic properties
Stability on
storage
Ageing for
3 months at
45°C
6-4 INV 11,550
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable –
Nothing to
report
6-5 INV 9,230
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable –
Nothing to
report
6-6 INV 10,140
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable –
Nothing to
report
6-7 O-IN 16,200
* Preparation Stable
* Organoleptic:
Spread: Nothing to report
Texture: grainy
Smell: Nothing to report
Color: Nothing to report
Surface: non-smooth
Conclusion: slightly
unstable
Sedimentation
- Bleeding
* NA: not applicable
Table 6
The results of Table 6 show that the twin selection made on the choice of macromonomer on
the one hand, and on the copolymer’s molecular weight on the other leads to homogeneous
compositions characterized by a decrease in the viscosity (all values lower than 14,000 cPs)
which do not display any problems (generation of heterogeneities, precipitation, depletion...)
during the preparation of the mascara and which are stable on storage.
29
It can therefore be deduced that there is a good level of compatibility between the polymer of
the invention and the film-forming polymer used in a cosmetic formulation that comprises
10wt.% of iron oxide.
Example 7 - Variation of the amount of coloring mineral pigment in the cosmetic
composition
A waterproof mascara composition is prepared using the following ingredients (the figures in
the last column indicate the weights in grams):
Table 7
First of all, B-9, B-10, B-13, and possibly the polymer additive B-16 (3wt.% as is of the total
weight of the cosmetic composition) are blended (800 to 1,000 rpm for 60 minutes) at room
temperature.
Then, the compounds B-11, B-12, the film-forming polymer B-14 (14wt.% of the total
weight of the cosmetic composition), and B-15 are added. The mixture is homogenized. This
mixture of phase B is heated to 60°C.
A
A-1 Beeswax (Koster Keunen Inc) 5.00
A-2 Carnauba wax ( Koster Keunen Inc ) 5.00
A-3 Candelilla wax ( Koster Keunen Inc ) 3.00
A-4 Stearic Acid (Masso) 2.00
A-5 Glyceryl Stearate (Masso) 1.20
A-6 Isopropyl Palmitate (Stéarinerie Dubois) 3.00
A-7 Petrolatum 4.00
A-8 DC 245 (Dow Corning) 3.00
B
B-9 Carbopol® ETD 2050 (Lubrizol™) 0.10
B-10 Veegum® Ultra (R. T. Vanderbilt) 0.50
B-11 Phenonip® (Clariant) 0.90
B-12 Iron Oxide Black 34-PV-3069 (Emerald Hilton Davis) z
B-13 Deionized Water q.s.f. 100
B-14 Avalure UR 450 (Lubrizol™) 15.00
B-15 DC 193 Surfactant (Dow Corning) 64.00
B-16 Polymer additive as is 3.00
C C-16 triethanolamine (99%) q.s.f. pH
7.5
30
At the same time, all ingredients of the A phase (except the ingredient A-8) are blended and
the mixture is heated to 85°C. The ingredient A-8 is then added to this mixture.
The non-aqueous phase A is incorporated into the aqueous phase B and the blend is
homogenized. The water evaporated is restored. The pH is adjusted to 7.5 with ingredient C-
16.
The blend left to cool while stirring. A formulation of the oil-in-water type has thus been
prepared.
Test 7-1
This test represents the standard; it does not implement any additional B-16 ingredient
besides those mentioned in Table 7.
Test 7-2
This test represents the prior art and implements, as the B-16 ingredient a polymer made up
of 100% acrylic acid, entirely neutralized with sodium hydroxide, and having a weightaveraged
molecular weight of 4,500 g/mol.
Test 7-3
This test represents the invention and implements as a B16 ingredient a copolymer made up
of each of its monomers in the respective percentages:
a) 12.5% of methacrylic acid;
b) 87.5 % of a monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
- m = 15, n = 46;
- PO and EO designate respectively propylene oxide and ethylene oxide;
- R designates the methacrylate group;
- R’ represents hydrogen;
completely neutralized with sodium hydroxide, and having a weight-averaged molecular
weight Mw of 75,000 g/mol.
31
Test Z
(wt.%)
Brookfield
Viscosity
(cPs,20 rpm,25°C)
Preparation &
Organoleptic properties
Stability on
storage Ageing for
3 months at 45°C
7-1
REF
3 15,270
* Preparation: Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable – Nothing
to report
12 120,310
* Preparation: Stable
* Organoleptic:
Spread: Nothing to report
Texture: grainy
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: slightly unstable
Beginning of
sedimentation
25 Not measurable NA Not measurable
7-2
PA
3 Not measurable
* Preparation: unstable
Flocculation & Depletion
* Organoleptic: NA
Conclusion: Unstable
NA
12 Not measurable
* Preparation: unstable
Flocculation & Depletion
* Organoleptic: NA
Conclusion: Unstable
NA
25 Not measurable
* Preparation: unstable
Flocculation & Depletion
* Organoleptic: NA
Conclusion: Unstable
NA
7-3
INV
3 10,810
* Preparation: Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable – Nothing
to report
12 60,180
* Preparation: Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable – Nothing
to report
25 112,180
* Preparation: Stable
* Organoleptic:
Spread: Nothing to report
Texture: Nothing to report
Smell: Nothing to report
Color: Nothing to report
Surface: Nothing to report
Conclusion: Stable
Stable – Nothing
to report
Table 8
32
The results of Table 8 show that using the copolymer of the invention in a waterproof
mascara formulation makes it possible to homogenize and to reduce the viscosity while
maintaining stability in the course of the implementation and of the ageing test; this also
applies to the formulations comprising 12% and 25% by weight of iron oxides.
Therefore, it can be deduced that there is a good level of compatibility between the polymer
of the invention and the film-forming polymer.
33
WE CLAIM:
1. Use of a water-soluble comb-type copolymer, made up of:
a) at least one anionic monomer having a polymerizable vinyl group and a
carboxyl moiety, and
b) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
m and n are integers other than zero and less than or equal to 150,
PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
R designates a polymerizable unsaturated group,
R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
said copolymer has a molecular weight between 20,000 and 400,000 g/mol, to
homogenize cosmetic compositions for makeup and/or for the care of keratinous
material comprising a film-forming polymer and a coloring pigment and/or a
pearlescent pigment.
2. Use according to claim 1, wherein the copolymer is made up of:
a) at least one monomer of (meth)acrylic acid and
b) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
m and n are integers other than zero and lower than 150,
PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
R designates a polymerizable unsaturated group,
34
R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
the molecular weight of said copolymer being between 20,000 g/mol and 250,000
g/mol.
3. Use according to claim 1 or 2, in which said coloring pigment is chosen from the
group that includes iron oxides, chromium oxides, zirconium oxides, zinc or cerium
oxides, manganese purple, blue ultramarine, carbon black, chromium hydrate, and
iron blue.
4. Use according to any one of the previous claims, in which the copolymer is made up
of, expressing the percentage by weight of each of its components:
a) 5% to 30% of at least one monomer of (meth)acrylic acid;
b) 70% to 95% at least one macromonomer having the formula (I);
c) 0% to 20% of at least one monomer which is an ester of (meth)acrylic acid;
where the sum of the percentages a), b), and c) is 100%.
5. Use according to any one of the previous claims, in which the copolymer is made up
of, expressing the percentage by weight of each of its components:
a) 5% to 15% of at least one monomer of (meth)acrylic acid;
b) 85% to 95% at least one macromonomer having the formula (I);
c) 0% to 10% of at least one monomer which is an ester of (meth)acrylic acid;
where the sum of the percentages a), b), and c) is 100%.
6. Use according to any of the previous claims, in which the comb-type (meth)acrylic
copolymer has a molecular weight between 30,000 and 380,000 g/mol, for example
between 30,000 g/mol and 150,000 g/mol.
7. Use according to any one of the previous claims, whereby said cosmetic composition
comprises 3 to 25 wt% of coloring pigments and/or pearlescent pigments and 8 to 15
wt% of film-forming polymer.
8. Use according to any one of the previous claims, wherein m and n are between 10 and
90 in formula (I).
35
9. Cosmetic composition for makeup and/or for the care of keratinous material,
comprising:
a) from 1 to 30 wt.% of pearlescent and/or coloring pigment;
b) from 0.1 to 30 wt.% of film-forming polymer; and
c) from 0.05 to 8 wt.% of a comb-type water-soluble copolymer made up of:
c1) at least one anionic monomer having a polymerizable vinyl group and a
carboxyl moiety, and
c2) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
m and n are integers other than zero and lower than 150;
PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
R designates a polymerizable unsaturated group,
R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
the molecular weight of said copolymer being between 20,000 g/mol and 400,000
g/mol.
10. Cosmetic composition according to claim 9, comprising:
a) from 1 to 30 wt.% of coloring mineral pigment;
b) from 0.1 to 30 wt.% of film-forming polymer; and
c) between 0.5 to 8 wt.% of comb-type (meth)acrylic copolymer made up of:
c1) at least one monomer of (meth)acrylic acid and
c2) at least one macro-monomer having the formula (I):
R – (PO)m – (EO)n – R’ (I)
wherein:
m and n are integers other than zero and lower than 150;
PO and EO designate respectively propylene oxide and ethylene oxide and are
arranged either randomly or in a regular pattern;
R designates a polymerizable unsaturated group,
36
R’ is hydrogen or an alkyl group having 1-4 carbon atoms;
the molecular weight of said copolymer being between 20,000 g/mol and 250,000
g/mol.
11. Cosmetic composition according to any one of the claims 9 or 10, comprising 1 to
80wt.% of volatile or non-volatile wax or oil.
12. Cosmetic composition according to any one of the claims 9 to 11, comprising 2 to
5wt.% of said copolymer.
13. Cosmetic composition according to any one of the claims 9 to 12, comprising 0.1% to
15wt.% of an aqueous-phase thickening agent.
14. Cosmetic composition according to anyone of the claims 9 to 13, comprising 0.5% to
20wt.% of a film-forming polymer.
15. Cosmetic composition according to anyone of the claims 9 to 14, comprising at least
one other additive chosen from a group consisting of reflective particles, surfactants
or emulsifiers, emollients, humectants, hydrating agents, neutralizing, acidifying, or
alkalizing agents, preservatives, fillers, antioxidants, perfumes, plasticizers, cosmetic
active ingredients, and sunscreens.