(en)The invention relates to a application system for coating, in particular, for making up, keratin fibers, having a reservoir containing a composition for coating, in particular, for making up keratin fibers, in particular, the eyelashes, a removable closure means designed to close the reservoir and an applicator member for applying the composition to the fibers, wherein the coating composition has an aqueous medium and a film-forming polyurethane in the form of solid particles dispersed in the aqueous medium, the composition having a viscosity, measured at 25° C., at a shear rate of 200 s −1 , ranging from 5 Pa·s to 18 Pa·s, and wherein the composition is free of wax.

1.ApplicationNumber: US-46039399-A
1.PublishNumber: US-6375941-B1
2.Date Publish: 20020423
3.Inventor: PIOT BERTRAND
de La Poterie Valérie
AUGUSTE FRéDERIC
BODELIN SOPHIE

4.Inventor Harmonized: PIOT BERTRAND(FR)
DE LA POTERIE VALERIE(FR)
AUGUSTE FREDERIC(FR)
BODELIN SOPHIE(FR)

5.Country: US
6.Claims:
(en)The invention relates to a application system for coating, in particular, for making up, keratin fibers, having a reservoir containing a composition for coating, in particular, for making up keratin fibers, in particular, the eyelashes, a removable closure means designed to close the reservoir and an applicator member for applying the composition to the fibers, wherein the coating composition has an aqueous medium and a film-forming polyurethane in the form of solid particles dispersed in the aqueous medium, the composition having a viscosity, measured at 25° C., at a shear rate of 200 s −1 , ranging from 5 Pa·s to 18 Pa·s, and wherein the composition is free of wax.

7.Description:
(en)The present invention relates to a product for coating, in particular, for making up, keratin fibers, in particular, human eyelashes and hair, comprising a polyurethane. The invention also relates to a process for coating, in particular, for making up, keratin fibers. The make-up product and process, according to the invention are more particularly intended for essentially longilinear keratin fibers such as the eyelashes, the eyebrows and the hair, including false eyelashes and wigs. The product of the invention can be a make-up product, a make-up base, a composition to be applied on or over make-up, named a topcoat, or a cosmetic treatment product for keratin fibers. The invention relates more particularly to a mascara.
Mascaras are commonly prepared as wax-based formulations according to two types: aqueous mascaras, known as cream mascaras, in the form of an emulsion of waxes in water; and anhydrous mascaras or mascaras with a low water content, known as waterproof mascaras, in the form of dispersions of waxes in solvents.
However, the film of make-up obtained with the inventive composition applied to eyelashes has a tendency to crumble over time; grains become deposited and leave marks around the eyes. Furthermore, the film thus embrittled is not resistant to rubbing, in particular, by the fingers, and/or to water, for example, when bathing or taking a shower. The make-up is thus not resistant and has poor staying power over time.
It is known to use, with the waxes, film-forming polymers which can be dissolved or dispersed in an aqueous medium, as described, in particular, in French Patent Application No. FR-A-2,528,699 and European Patent Application No. EP-A-655,234. However, the presence of waxes leads to poor staying power of the make-up over time, especially with respect to water and rubbing.
An object of the present invention,is thus to provide a mascara composition leading to a make-up effect that has good staying power over time.
The inventors have obtained such a mascara with a composition free of wax and comprising a film-forming polyurethane. The composition, which is easy to apply, coats the eyelashes well. The make-up effect is natural, comfortable and has good staying power over time; the film does not crumble after a day and is easy to remove with water, in particular, warm water.
More specifically, a subject of the invention is a system or product for coating, in particular, for making up, keratin fibers, comprising a reservoir containing a composition for coating, in particular, for making up, keratin fibers, especially the eyelashes, an applicator member and a removable closure means designed to close the reservoir, wherein the coating composition comprises an aqueous medium and a film-forming polyurethane in the form of solid particles dispersed in the aqueous medium, the composition having a viscosity, measured at 25° C., at a shear rate of 200 s −1 , ranging from 5 Pa·s (50 poises) to 18 Pa·s (180 poises), the composition furthermore being free of wax.
Another subject of the invention is a process for coating, in particular, for making up, keratin fibers, especially the eyelashes, wherein a coating composition, in particular, a make-up composition of the system defined above is applied along the length of the keratin fibers.
Another subject of the invention is the use of a coating composition, in particular, a make-up composition, as defined above, to obtain a coating, in particular, a make-up effect which has good staying power and/or which can be removed with water.
Additional features and advantages of the invention are set forth in the description that follows, and, in part, will be apparent from the description or may be learned from practice of the invention. The advantages of the invention will be realized and attained by the compositions, systems, and processes particularly pointed out in the written description and claims.
Both the foregoing general description and the following detailed description of the invention are exemplary and explanatory only and are not restrictive of the claimed invention.
In the present patent application, the expression “wax-free composition” means a composition that does not contain any compound solid at room temperature (25° C.), and that has a melting point ranging from 45° C. to 110° C.
The polyurethane used according to the invention can advantageously be chosen from polyester-polyurethanes, acrylic-polyurethanes, polyether-polyurethanes, and siliconed-polyurethanes. The polyurethane can preferably be an anionic polyurethane.
According to a first embodiment of the invention, the polyurethane can have a water uptake of less than or equal to 30%, and, in particular, ranging from 0.5% to 15%. The polyester-polyurethanes according to the invention have such water uptake properties. Such polyurethanes make it possible to obtain a make-up product having good staying power over time, in particular, for more than one day, or even two to three days, and good water-resistance. Advantageously, polyurethanes, and, in particular, polyester-polyurethanes, capable of forming a film having a hardness ranging from 40 to 200 seconds, and, better still, from 50 to 170 seconds, can be used.
According to the present application, the expression “water uptake of the polyurethane” means the percentage of water absorbed by the polyurethane after immersion in water at 30° C. for 10 minutes. The water uptake is measured for a layer 300 μm thick (before drying) deposited on a plate and then dried for 24 hours at 30° C. and at 50% relative humidity; pieces of about 1 cm 2 cut from the dry film are weighed (mass measurement M 1 ) and then immersed in water for 10 minutes. After immersion, the piece of film is dried to remove the excess surface water and then weighed (mass measurement M 2 ). The difference M 2 −M 1 corresponds to the amount of water absorbed by the polymer. The water uptake is equal to (M 2 −M 1 )/M 1 )×100, and is expressed as a percentage by weight of water relative to the weight of polymer.
The hardness of the polymer film is measured on a film obtained after drying, for 24 hours at 30° C. and at 50% relative humidity, of a layer 300 μm thick (before drying) of an aqueous dispersion containing 28% solids of the particles of radical-generated polymer. The hardness of the film is measured according to ASTM standard D-43-66, or standard NF-T 30-016 (October 1981), using a Persoz pendulum.
According to a second embodiment of the invention, the polyurethane can have a water uptake of greater than 30%, preferably from 30% to 150% and, better still, from 40% to 100%. The polyether-polyurethanes according to the invention have such water uptake properties. Such polyurethanes make it possible to obtain a make-up product which adheres well to the eyelashes, having good staying power over time and being easy to remove with water, in particular warm water at 35-45° C. Advantageously, polyurethanes and, in particular, polyether-polyurethanes, capable of forming a film having a hardness ranging from 10 to 40 seconds, and, better still, from 20 to 35 seconds, can be used.
The polyurethane particles dispersed in the aqueous medium of the composition generally have a size preferably ranging from 10 nm to 200 nm.
Polyester-polyurethanes that can be used are those sold under the names “Avalure UR-425”, “Avalure UR-430”, “Avalure UR-405” and “Avalure UR-410” by the company Goodrich, and “NEOREZ R-989” by the company Zeneca.
Polyether-polyurethanes that can be used are those sold under the names “Sancure 878”, “Avalure UR-450” and “Sancure 861” by the company Goodrich.
The term “acrylic-polyurethanes” means polyurethanes comprising at least one acrylic polymeric chain, or polyurethane/acrylic hybride polymers. Acrylic polyurethanes that can be used are those sold under the names “UCECOAT DW 5560, ” “UCECOAT DW 5561, ” “UCECOAT DW 5160, ” “UCECOAT DW 5460, ” and “UCECOAT DW 5660” by the company UCB, “FLEXTHANE 610, ” “FLEXTHANE 620, ” and “FLEXTHANE 630” by the company Air Products, and “SANCURE AU-4000” and “SANCURE XPD-2361” by the company Goodrich.
The polyurethane is present in the composition of the product according to the invention in an amount effective to form a film on the keratin fibers. The polyurethane can be present in the composition of the product according to the invention in a content, by weight of solids, ranging from 5% to 60% by weight relative to the total weight of the composition, preferably from 10% to 45% by weight, and, better still, from 15% to 35% by weight.
The aqueous medium of the composition can comprise water. It can also comprise a mixture of water and water-miscible solvent, such as lower monoalcohols containing from 1 to 5 carbon atoms, C 3 -C 4 ketones or C 3 -C 4 aldehydes. The water-miscible solvent is preferably ethanol. The content of water-miscible solvent can range from 0.1% to 15% by weight, and, better still, from 1% to 8% by weight, relative to the total weight of the composition.
Advantageously, the composition can have a viscosity ranging from 6 Pa·s (60 poises) to 15 Pa·s (150 poises), and, better still, from 7 Pa·s (70 poises) to 12 Pa·s (120 poises). Such a viscosity allows fast and easy application of the composition, as well as uniform coating over the entire length of the eyelashes. The viscosity is measured at 25° C. with a Rheomat RM 180 viscometer fitted with a No. 4 rotor, the measurement being carried out after spinning the rotor for 10 minutes (after which time stabilization of the viscosity and of the rotor spin speed are observed), at a shear rate of 200 s −1 .
To give the composition according to the invention the viscosity required for application to keratin fibers, and, in particular, the eyelashes, the composition can comprise a thickener for adjusting the desired viscosity.
Examples of thickeners that can be used according to the invention, include:
cellulose-based thickeners, for example, water-soluble cellulose-based thickeners, such as hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose and carboxymethylcellulose. Among these thickeners, preferred examples include the gums sold under the name “Cellosize QP 4400 H” by the company Amerchol,
guar gum, in particular, those sold under the name Vidogum GH 175 by the company Unipectine and under the name Jaguar C by the company Meyhall,
the quaternized guar gum sold under the name “Jaguar C-13-S” by the company Meyhall,
nonionic guar gums comprising C 1 -C 6 hydroxyalkyl groups. Mention may be made, for example, of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. Such guar gums are sold, in particular, under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP120 and Jaguar HP 105 by the company Meyhall, or under the name Galactasol 40H4FD2 by the company Aqualon,
xanthan gum, carob gum, scleroglucan gum, gellan gum, rhamsan gum and karaya gum,
alginates, maltodextrin, starch and its derivatives, hyaluronic acid and its salts,
clays, and, in particular, montmorillonites, hectorites and laponites,
crosslinked polyacrylic acids, such as the “Carbopol” products from the company Goodrich,
the polyglyceryl (meth)acrylate polymers sold under the names “Hispagel” or “Lubragel” by the companies Hispano Quimica or Guardian,
polyvinylpyrrolidone,
polyvinyl alcohol,
crosslinked acrylamide polymers and copolymers, such as those sold under the names “PAS 5161” or “Bozepol C” by the company Hoechst, “Sepigel 305” by the company SEPPIC,
crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymers sold under the name “Salcare SC95” by the company Allied Colloid, and
associative polymers and, in particular, associative polyurethanes.
In the composition according to the invention, the thickener can be present in an effective amount for the composition to have the viscosity as defined above. The thickener content can range, for example, from 0.1% to 10% by weight relative to the total weight of the composition, and preferably from 0.5% to 5% by weight.
The composition can also comprise other ingredients usually used in cosmetics. Such ingredients can be chosen, in particular, from plasticizers, coalescence agents, fillers, dyestuffs, such as pigments or dyes, surfactants, preserving agents, oils, cosmetic agents, such as moisturizers and anti-UV agents that are well known in the prior art. Needless to say, a person skilled in the art will take care to select this or these optional additives and/or the amount thereof, such that the advantageous properties of the make-up product are conserved.
Fillers that can be used, in particular, are the fillers usually used in mascara compositions. It is possible, for example, to use fumed silica, in particular, to obtain a thicker make-up effect on the eyelashes. Fillers particularly preferred for the composition according to the invention are, in particular, starch, such as rice starch, talc and polytetrafluoroethylene; these fillers are highly compatible with the aqueous medium of the composition and are easy to incorporate into the composition. In addition, they allow a smooth, shiny film of make-up to be obtained.
The fillers can be present in the composition in a content ranging from 0.1% to 6% by weight relative to the total weight of the composition.
The composition can also comprise an auxiliary film-forming polymer, to allow the cosmetic and physicochemical properties of the film of make-up to be modified. This auxiliary film-forming polymer can be in dissolved form or in the form of solid particles dispersed in the aqueous medium of the composition.
Examples of auxiliary film-forming polymers include vinyl polymers and, in particular, acrylic polymers, or, alternatively, polyesters, such as polyesters containing a sulphonic group.
The coating composition, in particular, the make-up composition, could be packaged in an application system comprising a reservoir containing the composition. The system could include a number of additional components. For example, the system could include a removable closure for closing the reservoir, preferably in a leaktight manner. The application system could also comprise an applicator member configured to apply the make-up composition to the keratin fibers, and, in particular, to the eyelashes. The applicator member is preferably configured to be loaded with the composition and then used to deposit the composition on the eyelashes. In a preferred embodiment, the applicator member is integral with the closure of the system.
The application system could also comprise a wiper for wiping excess composition from the applicator member. The wiper could be integral with the reservoir and configured to wipe the applicator member upon removal of the applicator member from the reservoir.
The applicator member could be a type of applicator configured to apply a substance to keratin fibers. Preferably, the applicator member could be a mascara brush well known to those skilled in the art. The applicator member preferably comprises bristles arranged radially around a twisted core, such as a metal core. The brush can be of varied shapes and can comprise cutout sections. Mascara brushes are described, for example, in French Patent Application No. FR-A-2,607,373 and European Patent Application Nos. EP-A-611,170, EP-A-811,336, EP-A-811,337 and EP-A-842,620, the disclosures of which are incorporated herein by reference.
In one embodiment, the application system could comprise a reservoir containing a mascara composition as defined above, in combination with an applicator member. The applicator member could comprise an applicating portion provided at one end of a shaft. The other end of the shaft could be integral with a handle component optionally configured to resealably close the reservoir.
The application system could also comprise an annular wiper fixed into a neck of the reservoir. When the applicator member is placed in the reservoir, the shaft of the applicator member preferably passes through the wiper. During removal of the applicator member from the reservoir, the wiper is configured to wipe the shaft and/or the applicating surface. Advantageously, the wiper has at least one finger and is provided with a central passage orifice that can optionally be flocked. Such a device is described, in particular, in French Patent Application No. FR-A-2,705,876, the disclosure of which is incorporated herein by reference.
The invention is illustrated in greater detail in the examples below.
FIG. 1 is a longitudinal cross-sectional view of an embodiment of a mascara application system in accordance with the invention.
With reference to FIG. 1, a mascara application system 1 , including an applicator member 2 and a reservoir 3 , containing a mascara composition 6 having the composition of Example 1 explained below. The reservoir 3 preferably has a threaded neck 4 and a leak-proof seal 5 on the neck 4 . A wiper 7 is preferably positioned in the neck 4 . The wiper 7 is held in place by means of a flange 8 which cooperates with a recess 9 in the neck 4 . The wiper 7 is made, in a known manner, of a flexible, elastic material.
The applicator member 2 preferably comprises an applicating portion 10 fixed to one end of a shaft 11 . Preferably, a handle 12 is integral with another end of the shaft 11 opposite the applicating portion 10 . The applicating portion 10 is preferably configured like a mascara brush comprising, in a known manner, bristles distributed radially as a helical strip around a twisted core.
The handle 12 preferably includes threading 12 a which cooperates with threading 4 a of the neck 4 to form a removable lid for the reservoir 3 . Leaktight closure of the reservoir 3 is obtained by screwing the handle 12 onto the neck 4 until the handle 12 contacts the seal 5 .


The present invention is further illustrated by the following examples which are designed to teach those of ordinary skill in the art how to practice the invention. The following examples are merely illustrative of the invention and should not be construed as limiting the invention as claimed. Examples of mascara compositions that can be packaged in the application system described above are given below.
EXAMPLE OF COMPOSITIONS
Example 1
A mascara having the composition below was prepared:












Aqueous dispersion of polyester-polyurethane
35.8
g AM


containing 49% solids (Avalure UR-425 from


Goodrich)


Hydroxyethyl cellulose
1.82
g


(Cellosize QP 4400 H from Amerchol)


Fumed silica (Aerosil 200 from Degussa)
1.82
g


Ethanol
5
g


Propylene glycol
4.05
g


Citric acid
0.15
g


Pigments
4
g


Preserving agents qs


Water qs
100
g


























The mascara applied easily to the eyelashes and gave a make-up effect that had good staying power for at least one day, and even 2 to 4 days, that was resistant to rubbing with the fingers and could be removed with water.
The mascara was tested on a panel of 17 women: 12 women (70%) found that the mascara had a staying power on the eyelashes of at least 3 days after application.
Example 2
A mascara having the composition below was prepared:












Aqueous dispersion of polyester-polyurethane
24.5
g AM


containing 49% solids (Avalure UR-425 from


Goodrich)


Hydroxyethyl cellulose
1.9
g


(Cellosize QP 4400 H from Amerchol)


Fumed silica (Aerosil 200 from Degussa)
1
g


Ethanol
5
g


Propylene glycol
5
g


Pigments
5
g


Preserving agents qs


Water qs
100
g

























The mascara applied easily and adhered well to the eyelashes. The film of make-up coated the eyelashes well over their entire length and had good staying power over time. In addition, the mascara was removed with warm water at 35° C.
Example 3
A mascara having the composition below was prepared:









Aqueous dispersion of polyether-polyurethane
24.5
g AM

containing 35% solids (Sancure 878 from Goodrich)

Hydroxyethyl cellulose
1.82
g

(Cellosize QP 4400 H from Amerchol)

Fumed silica (Aerosil 200 from Degussa)
1
g

Ethanol
5
g

Propylene glycol
5
g

Black pigment
5
g

Preserving agents qs

Water qs
100
g























The polyether-polyurethane Sancure 878 could be replaced with the polyether-polyurethane Avalure UR-450 or Sancure 861 from Goodrich.
The mascara applied easily to the eyelashes and gave a natural make-up effect with good staying power. After two days, the mascara was removed with warm water at 35° C.
Example 4
A mascara having the composition below was prepared:












Aqueous dispersion of polyester-polyurethane
24.5
g AM


containing 49% solids (Avalure UR-425 from


Goodrich)


Hydroxyethyl cellulose
1.9
g


(Cellosize QP 4400 H from Amerchol)


Polytetrafluoroethylene powder
1
g


(Ceridust 9205F from Hoechst)


Ethanol
5
g


Propylene glycol
5
g


Pigments
5
g


Preserving agents qs


Water qs
100
g


























The mascara applied easily and adhered well to the eyelashes. The film of make-up coated the eyelashes well over their entire length and had good staying power over time. The film was also smooth and shiny.
Example 5
A mascara having the composition below was prepared:












Aqueous dispersion of polyester-polyurethane
24.5
g AM


containing 49% solids (Avalure UR-425 from


Goodrich)


Hydroxyethyl cellulose
1.9
g


(Cellosize QP 4400 H from Amerchol)


Rice starch
2
g


Ethanol
5
g


Propylene glycol
5
g


Pigments
5
g


Preserving agents qs


Water qs
100
g

























The mascara applied easily and adhered well to the eyelashes. The film of make-up had good staying power over time and was smooth and shiny. In addition, the mascara was removed with warm water.
Example 6
A mascara having the composition below was prepared:












Aqueous dispersion of polyester-polyurethane
24.5
g AM


containing 49% solids (Avalure UR-425 from


Goodrich)


Hydroxyethyl cellulose
1.9
g


(Cellosize QP 4400 H from Amerchol)


Talc (Luzenac 15 M 00 from Luzenac)
2
g


Ethanol
5
g


Propylene glycol
5
g


Pigments
5
g


Preserving agents qs


Water qs
100
g

























The mascara applied easily and adhered well to the eyelashes. The film of make-up had good staying power over time and was smooth and shiny.
Example 7 Comparative
A mascara not forming part of the invention, having the composition below, was prepared:












Aqueous dispersion of styrene/acrylate copolymer
27
g AM


containing 45% solids (Neocryl A 1070 from


Zeneca)


Hydroxyethyl cellulose
1.82
g


(Cellosize QP 4400 H from Amerchol)


Fumed silica (Aerosil 200 from Degussa)
1
g


Ethanol
5
g


Propylene glycol
5
g


Pigments
5
g


Preserving agents qs


Water qs
100
g

























After applying the composition to the eyelashes, it was found that the staying power of the film of mascara was not as good as that of the film of mascara obtained with the compositions of Examples 1 to 6.
The foregoing written description relates to various embodiments of the present invention. Numerous changes and modifications may be made therein without departing from the spirit and scope of the invention as defined