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| United States Patent | 4871530 |
| Link to this page | http://www.wikipatents.com/4871530.html |
| Inventor(s) | Grollier; Jean F. (Paris, FR);
Dubief; Claude (Le Chesnay, FR);
Cauwet; Daniele (Paris, FR) |
| Abstract | A cosmetic composition suitable for the treatment of the hair or of the
skin in the form of a delayed-foaming gel, which comprises, in a
cosmetically acceptable aqueous medium, at least one surface-active agent,
at least one heterobiopolysaccharide and at least one delayed-foaming
agent which is able to form a foam after the composition is spread on the
hair or the skin. |
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Title Information  |
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| Publication Date |
October 3, 1989 |
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| Filing Date |
March 19, 1987 |
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| Priority Data |
Mar 19, 1986[LU]86361 |
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Title Information  |
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References  |
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| *references marked with an asterisk below are user-added references |
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| Market Size |
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Market Review  |
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Technical Review  |
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Claims  |
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We claim:
1. A cosmetic composition suitable for the treatment of the hair or of the
skin in the form of a delayed-foaming gel, which consists essentially of
one surface-active agent, one heterobiopolysaccharide and one
delayed-foaming agent which is able to form a foam after the composition
is spread on the hair or the skin, in a cosmetically acceptable medium.
2. A composition according to claim 1 wherein the surface-active agent is
present in an amount of from 0.1 to 50% by weight, the
heterobiopolysaccharide is present in an amount of from 0.05 to 5% by
weight and the delayed-foaming agent is present in an amount of from 0.5
to 12% by weight, all the above amounts being relative to the total weight
of the composition.
3. A composition according to claim 1 wherein the heterobiopolysaccharide
is soluble in water and comprises at least glucose, mannose and glucuronic
or galacturonic acid units in its structure.
4. A composition according to claim 3 wherein the heterobiopolysaccharide
is a xanthane gum having a molecular weight of from 1,000,000 to
50,000,000 or biopolymer PS87 which comprises glucose, galactose, mannose,
fructose and glucuronic acid units in its structure produced by Bacillus
polymyxa, biopolymer S88 produced by the AZTCC 31554 strain of
Pseudomonas, biopolymer S130 produced by the strain Alcaligenes ATCC
31555, biopolymer S 198 comprising rhamnose, glucose, mannose, and
glucuronic acid units in its structure produced by the strain Alcaligenes
ATCC 31853, biopolymer S 139 comprising rhamnose, glucose, mannose,
galactose and galacturonic acid units in its structure produced by the
strain Pseudomonas ATCC 31644 or an exocellular biopolymer produced by the
gram-positive or negative species of bacteria, yeast or fungi.
5. A composition according to claim 1 wherein the delayed-foaming agent is
at least one C.sub.3 -C.sub.6 aliphatic hydrocarbon.
6. A composition according to claim 5 wherein the delayed-foaming agent is
propane, n-butane, isobutane, isobutylene, n-pentane, isopentane, n-hexane
or 2-hexene.
7. A composition according to claim 1 wherein the delayed-foaming agent is
a completely or partially halogenated hydrocarbon.
8. A composition according to claim 1 wherein the delayed-foaming agent has
a vapour pressure of 0.25.times.10.sup.5 to 10.sup.5 Pa s at a temperature
of 32.degree.-38.degree. C.
9. A composition according to claim 1 which additionally comprises an
electrolyte in an amount of from 0.25 to 8% by weight relative to the
total weight of the composition.
10. A composition according to claim 1 in the form of a shampoo wherein at
least one of the surface-active agents present therein has detergent
properties.
11. A composition according to claim 1 in the form of a rinsing product
intended to be applied before or after shampooing, before or after dyeing
or bleaching, before or after permanent waving or hair-straightening, as a
hairdressing, conditioning or hair-setting gel.
12. A composition according to claim 1 in the form of a shaving gel which
additionally comprises at least one water-soluble soap in an amount of
from 4 to 25% by weight relative to the total weight of the composition.
13. A composition according to claim 1 which comprises, in an aqueous
medium:
(a) a xanthane gun,
(b) a C.sub.3 -C.sub.6 aliphatic hydrocarbon,
(c) an electrolyte,
(d) a cationic surface-active agent product of formula
##STR26##
in which R.sub.1 is a mixture of alkenyl and/or alkyl groups containing
from 14 to 22 carbon atoms derived from tallow fatty acids, R.sub.2,
R.sub.3 and R.sub.4 are all methyl groups, or R.sub.1 is a C.sub.16
H.sub.33 group, R.sub.2 and R.sub.3 are both methyl groups and R.sub.4 is
a Ch.sub.2 CH.sub.2 OH group or a methyl group, and
(e) a quaternized polysiloxane, quaternized protein or quaternary
polyammonium polymer as defined in paragraphs (1), (2), (3), (9), (10) or
(13) in claim 17 or as defined in claim 18 or a polymer comprising units
of formula:
##STR27##
in which X is a halogen, or poly(dimethylbutenylammonium chloride),
-bis(triethanolammonium chloride) or
poly(methacrylamidopropyltrimethylammonium chloride).
14. A composition according to claim 1 which comprises, in a cosmetically
acceptable aqueous medium,
(a) a cationic surface-active agent product of formula:
##STR28##
in which R is a mixture of alkenyl and/or alkyl groups containing from 14
to 22 carbon atoms derived from tallow fatty acids and R.sub.2, R.sub.3
and R.sub.4 are all methyl groups or R.sub.1 is a C.sub.16 H.sub.33 group
and R.sub.2 and R.sub.3 are both methyl groups and R.sub.4 is a CH.sub.2
CH.sub.2 OH group or a methyl group;
(b) a xanthane gum,
(c) pentane or isopentane, and
(d) a quaternary polysiloxane or quaternary protein having a molecular
weight of from 1,500 to 10,000 of formula (III):
##STR29##
in which A is a protein residue derived from collagen protein
hydrolysate, R.sub.5 is a lipophile group containing up to 30 carbon atoms
and R.sub.6 is an alkylene group containing from 1 to 6 carbon atoms.
15. A composition according to claim 1 which additionally comprises a
perfume, colorant, preserving agent, sequestering agent, softening agent
or sunscreen.
16. A cosmetic hair or skin treatment which comprises applying at least one
composition as defined in claim 1 to the skin or the hair in the form of a
nonfoaming gel from an aerosol device and forming a foam on the hair or
the skin by the mechanical action of spreading.
17. A cosmetic composition suitable for the treatment of the hair or the
skin in the form of a delayed-forming gel, which consists essentially of
one cationic surface-active agent, one heterobiopolysaccharide, and one
delayed-foaming agent in a cosmetically acceptable medium.
18. A composition according to claim 17 wherein the cationic surface-active
agent is either a product of formula:
##STR30##
in which R.sub.1 is a mixture of alkenyl and/or alkyl groups containing
from 10 to 22 carbon atoms derived from tallow, copra or soya fatty acids
or a C.sub.12 alkyl group and R.sub.2, R.sub.3 and R.sub.4 are identical
and are methyl groups or alternatively R.sub.1 is a C.sub.16 H.sub.33
group, and R.sub.2 and R.sub.3 are methyl groups and R.sub.4 is a
--CH.sub.2 --CH.sub.2 --OH group or a methyl group;
or a compound of formula:
##STR31##
19. A composition suitable for the treatment of the hair or the skin, in
the form of a delayed-foaming gel, which consists essentially of one
surface-active agent, one heteropolysaccharide, one delayed-foaming agent
in a cosmetically acceptable medium, and one cosmetically useful cationic
polymer containing primary, secondary, tertiary and/or quaternary amine
groups, having a molecular weight of from 500 to 5,000,000, in a
cosmetically acceptable medium. pg,46
20. A composition according to claim 19 wherein the cationic polymer is a
quaternized protein comprising a polypeptide which is chemically modified
to carry at least one quaternary ammonium group at the end of the chain or
grafted onto the chain.
21. A composition according to claim 20 wherein the quaternized protein is
a collagen hydrolysate bearing triethylammonium groups, a collagen
hydrolysate bearing trimethylammonium or trimethylstearylammonium chloride
groups, a protein hydrolysate bearing trimethylbenzyllammonium groups, a
protein hydrolysate bearing, on the polypeptide chain, quaternary ammonium
groups containing at least one alkyl group containing from 1 to 18 carbon
atoms, a quaternized protein having a molecular weight of from 1500 to
10,000 of formula:
##STR32##
in which A is a protein residue derived from collagen protein hydrolysate,
R.sub.5 is a lipophile group containing up to 30 carbon atoms, and R.sub.6
is an alkylene group containing from 1 to 6 carbon atoms.
22. A composition according to claim 19 wherein the cationic polymer is a
cationic silicone polymer.
23. A composition according to claim 22 wherein the cationic silicone
polymer is:
a polymer of formula:
##STR33##
in which x' and y' are each integers such that the molecular weight of
the polymer is from 5000 to 10,000,
a polymer of formula:
##STR34##
in which G is hydrogen, a phenyl group, a hydroxy group or a C.sub.1
-C.sub.8 alkyl group; a is from 0 to 3; b is from 0 to 1; n +m is from 1
to 2000; n is from 0 to 1999, m is from 1 to 2000 and R' is a monovalent
group of formula:
C.sub.q H.sub.2q L
in which q is an integer from 2 to 8 and L is a group chosen from:
##STR35##
in which R' is hydrogen, a phenyl group, a benzyl group or a monovalent
saturated hydrocarbon group containing from 1 to 20 carbon atoms and A is
a halogen; or
a polymer of formula:
##STR36##
in which R.sub.7 is a monovalent hydrocarbon group containing from 1 to
18 carbon atoms, R.sub.8 is a divalent hydrocarbon group or a divalent
C.sub.1 -C.sub.18 alkyleneoxy group, Q.sup.- is a halide anion, r is a
mean statistical value from 2 to 20, and s is a mean statistical value
from 20 to 200, all the above polymers either being block copolymers or
random copolymers.
24. A composition according to claim 19 wherein the cationic polymer is:
(1) a quaternized or unquaternized vinylpyrrolidone/dialkylaminoalkyl
acrylate or methacrylate copolymer;
(2) a cellulose ether derivative comprising quaternary ammonium groups;
(b 3) a cellulose or cellulose derivative copolymer grafted with a
water-soluble quaternary ammonium monomer;
(4) a cationic polysaccharide;
(5) a polymer comprising piperazinyl repeat units and divalent alkylene or
hydroxyalkylene groups with straight or branched chains optionally
interrupted by oxygen, sulphur or nitrogen or by aromatic or heterocyclic
rings, or an oxidation and/or quaternization product of these polymers;
(6) a water-soluble polyaminopolyamide which is a polycondensate of an
acidic compound with a polyamine, optionally crosslinked with an
epihalohydrin, a diepoxide, a dianhydride, an unsaturated anhydride, a
bis-unsaturated derivative, a bishalohydrin, a bisazetidinium, a
bishaloacyldiamine or an alkyl bishalide or again with an oligomer
resulting from the reaction of a difunctional compound reactive towards a
bishalohydrin, a bisazetidinium, a bishaloacyldiamine, an alkyl bishalide,
an epihalohydrin, a diepoxide or a bis-unsaturated derivative, the
crosslinking agent being employed in an amount of from 0.025 to 0.35 mole
per amine group of the polyaminopolyamine, or an alkylated or quaternized
derivative thereof;
(7) a polyaminopolyamide derivative produced from the condensation of a
polyalkylenepolyamine with a polycarboxylic acid followed by an alkylation
using a difunctional agent;
(8) a product of the reaction of a polyalkylenepolyamine containing two
primary amine groups and at least one secondary amine group with a
dicarboxylic acid or a saturated aliphatic dicarboxylic acid containing
from 3 to 8 carbon atoms, the molar ratio between the
polyalkylenepolyamine and the dicarboxylic acid being from 0.8:1 to 1.4:1,
the thus produced polyamino amide subsequently being reacted with
epichlorohydrin in a molar ratio of epichlorohydrin to the secondary amine
groups in the polyaminoamide of from 0.5:1 to 1.8:1;
(9) a cyclopolymer which is a homopolymer comprising repeat units of
formulae (IX) or (IX')
##STR37##
in which l and t are 0 to 1 and the sum l+t is 1, R.sub.12 is hydrogen or
a methyl group, R.sub.10 and R.sub.11 are each, independently of each
other, an alkyl group containing from 1 to 22 carbon atoms, a hydroxyalkyl
group or a lower amidoalkyl group, R.sub.10 and R.sub.11, together with
the nitrogen atom to which they are attached, are a heterocyclic group,
and Y.sup..crclbar. is an anion, or a copolymer comprising units of
formula (IX) or (IX') and units derived from acrylamide or
diacetoneacrylamide;
(10) a quaternary ammonium polymer comprising recurrent repeat units of
formula:
##STR38##
in which R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are each,
independently of each other, an aliphatic, alicyclic or arylaliphatic
group containing from 1 to 20 carbon atoms or a lower aliphatic
hydroxyalkyl group; or R.sub.13 and R.sub.14 and R.sub.15 and R.sub.16
together or separately form, with the nitrogen atoms to which they are
attached, a heterocyclic ring which optionally contains a second
heteroatom other than nitrogen; or R.sub.13, R.sub.14, R.sub.15 and
R.sub.16 are each, independently of each other, a linear or branched
C.sub.2 -C.sub.6 alkyl group substituted by a nitrile, ester, acyl, amide
or
##STR39##
in which R.sub.17 is an alkylene group and D is a quaternary ammonium
group and A.sub.2 and B.sub.2 are each, independently of each other, a
polymethylenic group containing from 2 to 20 carbon atoms which is linear
or branched, saturated or unsaturated and which optionally contains,
linked to or inserted into the main chain, one or more aromatic rings or
one or more oxygen or sulphur atoms or SO, SO.sub.2, disulphide, amino,
alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups;
or
A.sub.2 and R.sub.13 and R.sub.15 may form, with the two nitrogen atoms to
which they are attached, a piperazine ring; and when A.sub.2 is a linear
or branched, saturated or unsaturated alkylene or hydroxyalkylene radical,
B.sub.2 may also be a group of formula:
--(CH.sub.2).sub.n --CO--D--OC--(CH.sub.2).sub.n--
in which D is
(a) a glycol residue of formula --O--Z--O-- in which Z is a linear or
branched hydrocarbon group or a group of formula:
##STR40##
in which x or y is an integer from 1 to 4 representing a specified and
unique degree of polymerization or any number from 1 to 4 representing an
average degree of polymerization; or
(b) a residue of a bis-secondary diamine;
(c) a residue of a bis-primary diamine of formula:
--NH--Y--NH--
in which Y is a linear or branched hydrocarbon group or a divalent group of
formula:
--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2
(d) a ureylene group of formula:
--NH--CO--NH--
(11) a quaternary polyammonium polymer comprising units of formula:
##STR41##
in which R.sub.18, R.sub.19, R.sub.20 and R.sub.21, are each,
independently of each other, hydrogen or a methyl, ethyl, propyl,
.beta.-hydroxyethyl, .beta.-hydroxypropyl or --CH.sub.2 CH.sub.2
(OCH.sub.2 CH.sub.2).sub.p OH group in which p is an integer of from 0 to
6, with the proviso that R.sub.18, R.sub.19, R.sub.20 and R.sub.21 are not
simultaneously hydrogen, x and y are each, independently of each other,
integers of from 1 to 6, m is an integer of from 0 to 34, X is a halogen
and A is the residue of a dihalide;
(12) a homopolymer or copolymer derived from acrylic or methacrylic acid
comprising units of formula:
##STR42##
in which R.sub.24 is hydrogen or a methyl group, A.sub.1 is a linear or
branched alkyl group containing from 1 to 6 carbon atoms or a hydroxyalkyl
group containing 1 to 4 carbon atoms, R.sub.25, R.sub.26 and R.sub.27 are
each, independently of each other, an alkyl group containing from 1 to 18
carbon atoms or a benzyl group, R.sub.22 and R.sub.23 are each,
independently of each other, hydrogen or an alkyl group containing from 1
to 6 carbon atoms, and X.sub.2.sup..crclbar. is a methosulphate anion or a
halide anion;
(13) a quaternary vinylpyrrolidone or vinylimidazole polymer; or
(14) a polyalkyleneimine, vinylpyridine or vinylpyridinium polymer, a
condensate of a polyamine with epichlorohydrin, a quaternary polyureylene
or a chitin derivative.
25. A composition according to claim 24 in which the cationic polymer is as
defined in paragraph (9) therein wherein R.sub.10 and R.sub.11 are each,
independently of each other, a hydroxyalkyl group in which the alkyl
moiety contains from 1 to 5 carbon atoms or is as defined in paragraph
(10) therein wherein D is a residue of a piperazine derivative.
26. An aerosol device for the treatment of the hair or the skin comprising
an aerosol container containing in the form of one delayed-foaming gel, a
composition which consists essentially of one surface-active, one
heterobiopolysaccharide, one delayed-foaming agent which is able to form a
foam after the composition is spread on the hair or the skin and, as a
propellant agent, one condensable gas which is a halogenated or
unhalogenated hydrocarbon or mixture thereof with a noncondensable gas, in
a cosmetically acceptable medium.
27. A device according to claim 26 which contains a jacket with a
diaphragm.
28. An aerosol device for the treatment of the hair or the skin comprising
an aerosol container containing, in the form of one delayed-foaming gel, a
composition which consists essentially of one surface-active agent, one
heterobiopolysaccharide, one delayed-foaming agent which is able to form a
foam after the composition is spread on the hair or the skin and, as a
propellant agent, one noncondensable gas which is insoluble in the
composition when under pressure, in a cosmetically acceptable medium.
29. A device according to claim 28 wherein the noncondensable propellant is
situated in the upper part of the aerosol and the device is equipped with
a dip tube so as to expel the composition under pressure through the dip
tube.
30. An aerosol device for the treatment of the hair or of the skin
comprising an aerosol container containing, in the form of a
delayed-foaming gel, a composition which consists essentially of one
surface-active agent, one heterobiopolysaccharide, one delayed-foaming
agent in a cosmetically acceptable medium, and one cosmetically useful
cationic polymer containing primary, secondary, tertiary and/or quaternary
amine groups, having a molecular weight of from 500 to 5,000,000 which is
able to form a foam after the composition is spread on the hair or the
skin and, as a propellant agent, one condensable gas which is a
halogenated or unhalogenated hydrocarbon or mixture thereof with a
noncondensable gas, in a cosmetically acceptable medium. |
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Claims  |
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Description  |
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The present invention relates to a cosmetic composition for hair and skin
treatment, packaged in a device under pressure and forming a
delayed-foaming gel.
Gelled delayed-foaming compositions are well known in the field of
cosmetics. These compositions, which take the form of gels, generally
include, in combination with active substances which are to be dispensed,
a delayed-foaming agent which is in the liquid-vapour state at the
temperatures of use under a relatively reduced pressure of the order of a
few bars.
A composition in the form of delayed-foaming gel is the name given to a
composition packaged under pressure in an aerosol device, which is
delivered, under the effect of a propellant, in the form of a nonfoaming
gel under static conditions but which, under the mechanical action due to
the spreading, generates a foam "in situ" on the hair or on the skin.
Cosmetic compositions in the form of delayed-foaming gels which are known
in the state of the art are aqueous and generally contain a foaming agent
which is called "delayed", in the presence of a thickening agent such as
carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose,
hydroxypropyl cellulose, a copolymer of acrylic acid and polyallyl sucrose
or polyoxyalkylenes or polyethylene glycol ethers.
There are also known anhydrous self-foaming compositions described in
particular in Canadian Patent Nos. 1,028,957, No. 1,029,306 and No.
1,021,264.
These compositions of the state of the art and containing, more
particularly, the abovementioned thickening agents have a number of
disadvantages. It has been found, in fact, that these compositions
presented problems of preservation of the self-foaming capacity during
storage and especially after an initial use of a part of the product
packaged as an aerosol. This appears to be due to the fact that the
so-called delayed-foaming agent separates out at the surface, and this
leads to a phase separation and a major loss of this foaming agent when
the product is first used. It is then found that the self-foaming property
under the mechanical action due to the spreading is diminished or
disappears.
To overcome this type of problem, some compositions of the prior art have
been dispensed from an aerosol device with a diaphragm as described in
U.S. Pat. No. 3,541,581, in which compositions the active ingredients
containing the foaming agent are separated from the propellant by means of
an extensible diaphragm. In this case, an intimate contact between the
active agents and the delayed-foaming agent must be produced by
preliminary mixing of the two components under pressure.
Furthermore, the applicant has tried to use, in such compositions, cationic
compounds which are known per se in the cosmetics industry for skin or
hair treatment. These compounds make it possible, in particular, to impart
good disentangling properties to hair and softness to the skin. It has
found that it was impossible to produce a stable and homogeneous mixture
by combining, in a gelled and aqueous delayed-foaming composition, the
abovementioned thickening agents for producing a gel with a cationic
compound and a delayed-foaming agent. The foaming agent separates out at
the surface and the remaining composition flows out as several phases, and
this leads to the formation of a gel which does not possess the desired
self-foaming properties.
The applicant has found, surprisingly, that by employing a water-soluble
heterobiopolysaccharide, the best known example of which is xanthane gum,
in these compositions, it was possible to overcome the abovementioned
disadvantages and to prepare, under good conditions, delayed-foaming
compositions in the form of an aqueous gel, preserving their
delayed-foaming properties during their storage, even after a first use.
Although this explanation is not intended to imply any limitation, this
result appears to be due essentially to the fact that the
heterobiopolysaccharide absorbs the delayed-foaming agent completely and
immediately and consequently prevents it from separating out.
This effect is especially remarkable in the case of the compositions which
additionally contain cationic compounds for hair or skin treatment. These
compositions are, in fact, homogeneous and stable, in contrast to what it
was possible to produce previously.
The compositions according to the invention have the advantage,
furthermore, of being capable of being prepared directly in the aerosol
packaging, avoiding the intermediate stage required in the previous
processes to promote the distribution of the delayed-foaming agent in the
composition by a preliminary mixing under pressure.
By virtue of the composition according to the invention, the
delayed-foaming gel can be prepared directly by introducing the
delayed-foaming agent into the aerosol device containing a diaphragm, that
is to say a jacket, following the introduction of the gelling agent and of
other active substances such as the surface and treatment agent. The
compositions according to the invention have the particularly attractive
advantage of remaining homogeneous and stable when kept in storage at
ambient temperature and at temperatures of up to 50.degree. C.
The compositions dispensed from the pressurized aerosol device form gels
which are initially nonfoaming and which, under the mechanical action such
as being spread on the hair or the skin by hand or by massage, generate an
abundant, stable and uniform foam which is essentially uniform from the
initial to the final use of the contents of the aerosol device.
The foam produced in this manner is particularly light and soft to the
touch, and this constitutes another advantage when compared with the foams
which could be produced according to the state of the art. It imparts more
sheen and softness to hair and more softness to the skin.
A subject of the invention is therefore a composition pressurized in an
aerosol device and intended to be used for the cosmetic treatment of hair
or of the skin, in the form of a delayed-foaming gel and containing at
least one delayed-foaming agent and a heterobiopolysaccharide.
Another subject of the invention is a process for the cosmetic treatment of
hair or of the skin by virtue of a composition of this kind.
Other subjects of the invention will become apparent from reading the
description and the examples which follow.
The cosmetic composition according to the invention, intended to be
employed for the cosmetic treatment of hair or of the skin is
characterized in that it is in the form of a delayed-foaming gel
containing, in a cosmetically acceptable aqueous medium, at least one
surface agent, at least one heterobiopolysaccharide and at least one
delayed-foaming agent said gel forming a foam after being spread on the
hair or the skin.
The surface agents present in the compositions are known per se and are
chosen from anionic, nonionic, amphoteric or cationic surface agents or a
mixture thereof. Their concentration is generally between 0.1 and 50% and
preferably between 0.5 and 20% based on the total weight of the
composition. As is well known, these agents may have detergent properties,
in which case the composition has hair or skin cleansing properties, in
addition to the cosmetic treatment properties.
A particularly attractive embodiment consists in the use of at least one
cationic surface agent in the composition. These cationic surface agents,
which are known per se, are chosen more particularly from the compounds
corresponding to the formula:
##STR1##
in which
(i) R.sub.1 denotes a mixture of alkenyl and/or alkyl radicals containing
from 10 to 22 carbon atoms derived from tallow, copra or soya fatty acids
or a C.sub.12 alkyl radical, the groups R.sub.2, R.sub.3 and R.sub.4
denoting a methyl group,
(ii) R.sub.1 denotes a C.sub.16 H.sub.33 group and R.sub.2 and R.sub.3
denote a CH.sub.3 group, R.sub.4 denoting a CH.sub.2 --CH.sub.2 --OH
group,
or alternatively all three R.sub.2, R.sub.3 and R.sub.4 denote a methyl
group,
X.sup..crclbar. denoting a halide anion and preferably Cl.sup..crclbar..
Other cationic surface agents which are preferentially employed in the
compositions according to the invention correspond to the formula (II)
##STR2##
in which X.sup..crclbar. denotes a halide anion and preferably
Cl.sup..crclbar..
These cationic surface-active agents are present in the compositions
according to the invention in proportions which are preferably between 0.1
and 5% and in particular between 0.5 and 3% by weight based on the total
weight of the composition.
The heterobiopolysaccharides employed in accordance with the invention are
known per se and are produced, in particular, by the fermentation of
sugars by microorganisms. These heterobiopolysaccharides generally
comprise glucose, mannose and glucuronic or galacturonic acid units in
their structure.
Among these heterobiopolysaccharides, those more particularly preferred are
the scleroglucanes or the xanthane gums produced by the action of the
bacterium Xanthomonas campestri and the mutants or variants thereof having
a molecular weight of between 1,000,000 and 50,000,000. The xanthane gums
have a viscosity of between 0.60 and 1.65 Pa s in the case of an aqueous
composition containing 1% of xanthane gum, measured with a Brookfield type
LVT viscometer at 60 revolutions/minute. In their structure, they comprise
3 different monosaccharides which are mannose, glucose and glucuronic
acid. Products which are particularly preferred are those marketed under
the trade name "Keltrol" by the Kelco company, a 1% aqueous solution of
which has a Brookfield LVT viscosity of 1.2 to 1.6 Pa s at 60
revolutions/minute, Kelzan S marketed by the Kelco company, a 1% aqueous
solution of which has a Brookfield LVT viscosity of 0.850 Pa s at 60
revolutions/minute, Rhodopol 23, 23 U and 23 C, which are marketed by the
Rhone-Poulenc company, a 0.3% aqueous solution of which has a Brookfield
LVT viscosity of 0.450.+-.0.050 Pa s at 30 revolutions/minute, Rhodigel 23
sold by the Rhone-Poulenc company, Deuteron XG marketed by the Schoener
GmbH company, a 1% aqueous solution of which has a viscosity of 1.200 Pa
s, measured with a Brookfield LVT viscometer at 30 revolutions/minute, the
scleroglucane sold under the trade name " Actigum CX9" by the Ceca company
which has a viscosity of 1.200 Pa s, measured with a Brookfield LVT
viscometer at 30 revolutions/minute in the case of a 1% aqueous solution
or the products sold by the Kelco company under the trade names "Kelzan K3
B130, K8 B12" whose Haake Rotovisco RV1, MV1 viscosity at 25.degree. C. is
1 Pa s at 10s.sup.-1 and K9 C57 whose viscosity of 1% aqueous solution is
from 0.63 to 1 Pa s, measured with a Brookfield LVS viscometer at 60
revolutions/minute.
Other heterobiopolysaccharides which may be employed in accordance with the
invention may be chosen from:
the biopolymer PS 87 generated by the bacterium Bacillus polymyxa which
comprises glucose, galactose, mannose, fucose and glucuronic acid in its
structure; this biopolymer PS 87 is described more particularly in the
published European Patent Application No. 23,397;
the biopolymer S88 generated by the strain Pseudomonas ATCC 31554 which
comprises rhamnose, glucose, mannose and glucuronic acid in its structure;
this biopolymer is described in British Patent No. 2,058,106;
the biopolymer S130 generated by the strain Alcaligenes ATCC 31555, which
comprises rhamnose, glucose, mannose and glucuronic acid in its molecule;
this biopolymer is described more particularly in British Patent
2,058,107;
the biopolymer S139 generated by the strain Pseudomonas ATCC 31644 which
comprises rhamnose, glucose, mannose, galactose and galacturonic acid in
its molecule; this biopolymer is described in particular in U.S. Pat. No.
4,454,316;
the biopolymer S198 generated by the strain Alcaligenes ATCC 31853, which
comprises rhamnose, glucose, mannose and glucuronic acid in its molecule;
this biopolymer i$ described in particular in European Patent Application
64,354; and
the exocellular biopolymer generated by the gram-positive or negative
species of bacteria, of yeasts, fungi or algae, which is described in
particular in German Patent Application No. 3,224,547.
These heterobiopolysaccharides are employed in the compositions according
to the invention in proportions which are preferably between 0.05 and 5%
by weight and more particularly between 0.1 and 2% by weight based on the
total weight of the composition.
The delayed-foaming agent present in the compositions according to the
invention is a C.sub.3-6 aliphatic hydrocarbon or mixtures thereof. It is
chosen more particularly from propane, n-butane, isobutane, isobutylene,
n-pentane, isopentane, n-hexane and 2-hexene.
Other delayed-foaming agents are chosen from partially or completely
halogenated hydrocarbons such as, more particularly,
trichlorotrifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane or
mixtures of these derivatives.
The particularly preferred compositions are those based on C.sub.3 -C.sub.6
hydrocarbons which are mentioned above. These products, which have
delayed-foaming properties, generally have a vapour pressure ranging from
0.25 10.sup.5 to 10.sup.5 Pa at a temperature of 32.degree.-38.degree. C.
The delayed-foaming agents are used in proportions preferably between 0.5
and 12% by weight and in particular between 1 and 5% by weight based on
the total weight of the composition.
A particularly advantageous embodiment of the invention is a composition
intended for the cosmetic treatment of hair in the form of a
delayed-foaming gel dispensed from an aerosol package with a diaphragm
containing, in an aqueous medium, a heterobiopolysaccharide, a cationic
surface agent and treatment agents chosen from cosmetically acceptable
polymers and the delayed-foaming agent.
The cosmetic polymers which are particularly preferred are cationic and are
chosen from polymers containing primary, secondary, tertiary and/or
quaternary amine groups forming part of the polymer chain or directly
linked to the latter, having a molecular weight of between 500 and
approximately 5,000,000.
Among these polymers there may be more particularly mentioned quaternized
proteins, quaternized polysiloxanes, and polymers of the polyamine,
polyaminoamide and quaternary polyammonium type. These polymers are
preferably present in proportions of between 0.25 and 3% by weight based
on the total weight of the composition.
The quaternized proteins are, in particular, polypeptides which are
chemically modified and which carry quaternary ammonium groups at the end
of the chain or grafted onto the latter. Among these proteins there may be
mentioned, in particular:
collagen hydrolysates bearing triethylammonium groups such as the products
sold under the trade name "Quat-Pro E" by the Maybrook company and called
"Triethonium Hydrolyzed Collagen Ethosulfate" in the CTFA dictionary;
collagen hydrolysates bearing trimethylammonium or trimethylstearylammonium
chloride groups sold under the trade name of Quat-Pro S by the Maybrook
company and called "Steartrimonium Hydrolyzed Collagen" in the CTFA
dictionary;
animal protein hydrolysates bearing trimethylbenzylammonium groups such as
the products sold under the trade name "Crotein BTA" by the Croda company
and called "Benzyltrimonium hydrolyzed animal protein" in the CTFA
dictionary; and
protein hydrolysates bearing, on the polypeptide chain, quaternary ammonium
groups containing at least one alkyl radical containing from 1 to 18
carbon atoms.
Among these protein hydrolysates there may be mentioned, among others:
Croquat L, whose polypeptide chain has a mean molecular weight of
approximately 2500 and whose quaternary ammonium group contains a C.sub.12
alkyl group;
Croquat M, whose polypeptide chain has a mean molecular weight of
approximately 2500 and whose quaternary ammonium group contains a C.sub.10
-C.sub.18 alkyl group;
Croquat S, whose polypeptide chain has a mean molecular weight of
approximately 2700 and whose quaternary ammonium group contains a C.sub.18
alkyl group; and
Crotein Q, whose polypeptide chain has a mean molecular weight of the order
of 12,000 and whose quaternary ammonium group contains at least one alkyl
group containing from 1 to 18 carbon atoms.
These various products are sold by the Croda company.
Other quaternized proteins are those corresponding to the formula:
##STR3##
which formula X.sup.- is an anion of an organic or inorganic acid, A
denotes a protein residue derived from collagen protein hydrolysates,
R.sub.5 denotes a lipophile group containing up to 30 carbon atoms,
R.sub.6 denotes an alkylene group containing 1 to 6 carbon atoms; these
proteins have a molecular weight of between 1500 and 10,000, preferably
2000 and 5000. The preferred products are those sold under the trade name
"Lexein QX 3000", called "Cocotrimonium Collagen Hydrolyzate" in the CTFA
dictionary, by the Inolex company.
Another group of cationic polymers are cationic silicone polymers. Among
these polymers there may be mentioned
(a) the quaternized polysiloxanes called "Amodimethicone" in the CTFA
dictionary and corresponding to the formula:
##STR4##
in which x' and y' are integers which depend on the molecular weight which
is generally between 5000 and 10,000;
(b) the cationic silicone polymers corresponding to the formula:
##STR5##
in which
G is a hydrogen atom or the phenyl group, OH, a C.sub.1 -C.sub.8 alkyl, and
preferably a methyl group,
a denotes 0 or an integer from 1 to 3 and preferably 0,
b denotes 0 or 1 and preferably 1,
the sum (n +m) is an integer from 1 to 2,000 and preferably from 50 to 150,
it being possible for n to denote a number from 0 to 1999 and preferably
from 49 to 149 and it being possible for m to denote an integer from 1 to
2000 and preferably from 1 to 10;
R' is a monovalent radical of formula C.sub.q H.sub.2q L in which q is a
number from 2 to 8 and L is chosen from the groups:
##STR6##
which R" may denote hydrogen, phenyl, benzyl, a monovalent saturated
hydrocarbon radical and preferably an alkyl radical containing from 1 to
20 carbon atoms and A.sup..crclbar. denotes a halide ion such a fluoride,
chloride, bromide or iodide.
A particularly advantageous product falling within this definition is the
polymer called "trimethylsilylamodimethicone" corresponding to the
formula:
##STR7##
in which n and m have the meanings given above (formula V). Polymers of
this kind are described in U.S. patent application 95,238 EP-A;
(c) the cationic silicone polymers corresponding to the formula:
##STR8##
in which
R.sub.7 denotes a monovalent hydrocarbon radical containing from 1 to 18
carbon atoms and in particular an alkyl or alkenyl and preferably methyl
radical;
R.sub.8 denotes a divalent hydrocarbon radical, preferably a C.sub.1
-C.sub.18 alkylene radical or a divalent C.sub.1 -C.sub.18 and preferably
C.sub.1 -C.sub.8 alkylenoxy radical;
Q.sup.- is a halide ion, preferably chloride;
r denotes a mean statistical value from 2 to 20 and preferably from 2 to 8;
s denotes a mean statistical value from 20 to 200 and preferably from 20 to
50.
Polymers of this kind are described more particularly in U.S. Pat. No.
4,185,087.
A particularly preferred polymer which is a member of this class is the
polymer sold by the Union Carbide company under the trade name "Ucar
Silicone ALE 56" which is characterized by a flash point of 60.degree. C.
according to the ASTM standard D-93, a viscosity of 0.011 Pa s at a
concentration of 35% of active substance and at 25.degree. C. and by a
total basicity index of 0.24 meq/g.
When these silicone polymers are employed, a particularly advantageous
embodiment is their use together with cationic surface agents or nonionic
surface agents. In the compositions according to the invention it is
possible to use, for example, the commercial product sold under the trade
name "Emulsion Cationique DC 929" by the Dow Corning company which
contains the amodimethicone of formula (IV), a cationic surface agent
corresponding to the formula:
##STR9##
in which R.sub.9 denotes a mixture of alkenyl and/or alkyl radicals
containing from 14 to 22 carbon atoms derived from tallow fatty acids, and
a nonionic surface agent of formula:
##STR10##
known under the trade name "Nonoxynol 10".
Another composition which may be employed in this embodiment of the
invention is the composition containing the product sold under the trade
name "Dow Corning Q2 7224" by the Dow Corning company containing a
combination of the trimethylsilylamodimethicone of formula (VI), a
nonionic surface agent of formula:
##STR11##
also called octoxynol-40, another nonionic surface agent of formula:
##STR12##
also called isolaureth-6 and glycol.
The polymers of the polyamine, polyaminoamide and quaternary polyammonium
type which can be employed in accordance with the present invention are
described in particular in the applicant's French Patent Nos. 82/07,996 or
84/04,475. Among these polymers, there may be mentioned:
(1) The vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate
copolymers, quaternized or otherwise, such as the products sold under the
trade name "Gafquat" by the GAF Corporation such as, for example, "Gafquat
734 or 755" or the product called "Copolymer 845". These polymers are
described in detail in French Patent Nos. 2,077,143 and 2,393,573.
(2) The cellulose ether derivatives containing quaternary ammonium groups
described in French Patent No. 1,492,597 and in particular the polymers
marketed under the trade names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR
400, LR 30M) by the Union Carbide Corporation. The polymers are also
defined in the CTFA dictionary as hydroxyethylcellulose quaternary
ammoniums which have reacted with an epoxide substituted by a
trimethylammonium group.
(3) Cationic cellulose derivatives such as cellulose copolymers or
cellulose derivatives grafted with a water-soluble quaternary ammonium
monomer and described in greater detail in U.S. Pat. No. 4,131,576, such
as hydroxyalkylcelluloses such as hydroxymethyl, hydroxyethyl or
hydroxypropyl cellulose grafted with a methacryloylethyltrimethylammonium,
methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
The commercial products corresponding to this definition are more
particularly the products sold under the trade name "Celquat L 200" and
"Celquat H 100" by the National Starch company.
(4) The cationic polysaccharides described more particularly in U.S. Pat.
Nos. 3,589,578 and 4,031,307 and more particularly the product marketed
under the trade name "Jaguar C. 13 S" sold by the Meyhall company.
(5) Polymers consisting of piperazinyl repeat units and of divalent
alkylene or hydroxyalkylene radicals containing straight or branched
chains interrupted, if desired, by oxygen, sulphur or nitrogen atoms or by
aromatic or heterocyclic rings, as well as the oxidation and/or
quaternization products of these polymers. Polymers of this kind are
described in French Patent Nos. 2,162,025 and 2,280,361.
(6) The water-soluble polyaminopolyamides prepared in particular by
polycondensation of an acidic compound with a polyamine. These
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