U.S. patent application number 09/750716 was filed with the patent office on 2001-09-27 for compositions for oxidation dyeing keratin fibers comprising at least one thickening polymer comprising at least one fatty chain and at least one fatty alcohol chosen from monoglycerolated fatty alcohols and polyglycerolated fatty alcohols.
Invention is credited to Cottard, Francois, Rondeau, Christine.
Application Number | 20010023514 09/750716 |
Document ID | / |
Family ID | 9554067 |
Filed Date | 2001-09-27 |
United States Patent
Application |
20010023514 |
Kind Code |
A1 |
Cottard, Francois ; et
al. |
September 27, 2001 |
Compositions for oxidation dyeing keratin fibers comprising at
least one thickening polymer comprising at least one fatty chain
and at least one fatty alcohol chosen from monoglycerolated fatty
alcohols and polyglycerolated fatty alcohols
Abstract
Compositions for oxidation dyeing of keratin fibers, in
particular human keratin fibers such as hair, comprising, in a
dyeing medium, at least one oxidation dye, at least one thickening
polymer comprising at least one fatty chain and at least one fatty
alcohol chosen from monoglycerolated and polyglycerolated fatty
alcohols. Processes comprising such oxidation dyeing
compositions.
Inventors: |
Cottard, Francois;
(Levallois-Perret, FR) ; Rondeau, Christine;
(Sartrouville, FR) |
Correspondence
Address: |
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW
GARRETT & DUNNER, L.L.P.
1300 I Street, N.W.
Washington
DC
20005-3315
US
|
Family ID: |
9554067 |
Appl. No.: |
09/750716 |
Filed: |
January 2, 2001 |
Current U.S.
Class: |
8/406 ;
8/421 |
Current CPC
Class: |
A61K 8/8147 20130101;
A61K 8/817 20130101; A61K 8/39 20130101; A61Q 5/10 20130101 |
Class at
Publication: |
8/406 ;
8/421 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 30, 1999 |
FR |
99 16757 |
Claims
What is claimed is:
1. A cosmetic composition for oxidation dyeing keratin fibers,
comprising, in a dyeing medium (1) at least one oxidation dye, (2)
at least one thickening polymer comprising at least one fatty
chain, and (3) at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols.
2. A composition according to claim 1, wherein said keratin fibers
are chosen from human keratin fibers.
3. A composition according to claim 2, wherein said human keratin
fibers are chosen from human hair.
4. A composition according to claim 1, wherein said at least one
fatty alcohol chosen from monoglycerolated and polyglycerolated
fatty alcohols is chosen from fatty alcohols of formula:
RO--(--CH.sub.2--CH(CH.sub.2OH)- --O--).sub.n--H in which: R is
chosen from linear and branched, saturated and unsaturated groups
comprising from 8 to 40 carbon atoms; and n is a number ranging
from 1 to 30.
5. A composition according to claim 4, wherein said R comprises
from 10 to 30 carbon atoms.
6. A composition according to claim 4, wherein said n is a number
ranging from 1 to 10.
7. A composition according to claim 1, wherein said at least one
fatty alcohol chosen from monoglycerolated and polyglycerolated
fatty alcohols is present in an amount ranging from 0.01% to 30% by
weight relative to the total weight of the composition.
8. A composition according to claim 7, wherein said at least one
fatty alcohol chosen from monoglycerolated and polyglycerolated
fatty alcohols is present in an amount ranging from 0.05% to 20% by
weight relative to the total weight of the composition.
9. A composition according to claim 8, wherein said at least one
fatty alcohol chosen from monoglycerolated and polyglycerolated
fatty alcohols is present in an amount ranging from 0.1% to 15% by
weight relative to the total weight of the composition.
10. A composition according to claim 1, wherein said at least one
thickening polymer comprising at least one fatty chain is chosen
from anionic, nonionic and cationic thickening polymers comprising
at least one fatty chain.
11. A composition according to claim 10, wherein said anionic
thickening polymers comprising at least one fatty chain comprise at
least one hydrophilic unit and at least one allyl ether unit
comprising at least one fatty chain.
12. A composition according to claim 11, wherein said at least one
hydrophilic unit is chosen from ethylenic unsaturated anionic
monomeric residues.
13. A composition according to claim 12, wherein said ethylenic
unsaturated anionic monomeric residues are chosen from residues of
vinylcarboxylic acid.
14. A composition according to claim 11, wherein said at least one
allyl ether unit comprising at least one fatty chain is chosen from
monomeric residues formed from monomers of formula (I):
CH.sub.2.dbd.C--R'--CH.sub.- 2--O--B.sub.n--R(I) in which R' is
chosen from H and CH.sub.3, B is an ethyleneoxy group, n is chosen
from zero and integers ranging from 1 to 100, R is a hydrocarbon
group comprising from 8 to 30 carbon atoms chosen from alkyl,
arylalkyl, aryl, alkylaryl, and cycloalkyl groups.
15. A composition according to claim 14, wherein said hydrocarbon
group comprises from 10 to 24 carbon atoms.
16. A composition according to claim 15, wherein said hydrocarbon
group comprises from 12 to 18 carbon atoms.
17. A composition according to claim 10, wherein said anionic
thickening polymers comprising at least one fatty chain comprise at
least one hydrophilic unit of the olefinic unsaturated carboxylic
acid type and at least one hydrophobic unit of the
(C.sub.10-C.sub.30)alkyl ester of unsaturated carboxylic acid
type.
18. A composition according to claim 17, wherein said at least one
hydrophilic unit of the olefinic unsaturated carboxylic acid type
is chosen from monomeric residues formed from monomers of formula
(II): 21in which R.sub.1 is chosen from H, CH.sub.3, and
C.sub.2H.sub.5, and wherein said at least one hydrophobic unit of
the (C.sub.10-C.sub.30)alky- l ester of unsaturated carboxylic acid
type is chosen from monomeric residues formed from monomers of
formula (III): 22in which R.sub.2 is chosen from H, CH.sub.3, and
C.sub.2H.sub.5, and R.sub.3 is chosen from C.sub.10-C.sub.30 alkyl
groups.
19. A composition according to claim 18, wherein said R.sub.3 is
chosen from C.sub.12-C.sub.22 alkyl groups.
20. A composition according to claim 10, wherein said anionic
thickening polymers comprising at least one fatty chain are chosen
from terpolymers of maleic anhydride/C.sub.30-C.sub.38
.alpha.-olefin/alkyl maleate.
21. A composition according to claim 10, wherein said anionic
thickening polymers comprising at least one fatty chain are chosen
from acrylic terpolymers comprising: (a) a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation (b) a nonsurfactant
monomer with .alpha.,.beta.-monoethylenic unsaturation different
from (a) (c) a nonionic monourethane which is the product of the
reaction of a monohydric surfactant with a monoisocyanate with
monoethylenic unsaturation.
22. A composition according to claim 10, wherein said anionic
thickening polymers comprising at least one fatty chain are chosen
from copolymers formed from at least two monomers, wherein at least
one of said at least two monomers is chosen from a carboxylic acid
with .alpha.,.beta.-monoethylenic unsaturation, an ester of a
carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation, and
an oxyalkylenated fatty alcohol.
23. A composition according to claim 10, wherein said nonionic
thickening polymer comprising at least one fatty chain is chosen
from: (1) celluloses modified by at least one group comprising at
least one fatty chain; (2) hydroxypropylguars modified by at least
one group comprising at least one fatty chain; (3) copolymers
formed from vinylpyrrolidone and at least one hydrophobic monomer
comprising at least one fatty chain; (4) copolymers formed from at
least one C.sub.1-C.sub.6 alkyl methacrylate and at least one
amphiphilic monomer comprising at least one fatty chain and
copolymers formed from at least one C.sub.1-C.sub.6 alkyl acrylate
and at least one amphiphilic monomer comprising at least one fatty
chain; (5) copolymers formed from at least one hydrophilic
methacrylate and at least one hydrophobic monomer comprising at
least one fatty chain and copolymers formed from at least one
hydrophilic acrylate and at least one hydrophobic monomer
comprising at least one fatty chain; (6) polyether-polyurethanes
comprising in their chain both hydrophilic sequences and
hydrophobic sequences; and (7) polymers comprising an aminoplast
ether backbone possessing at least one fatty chain.
24. A composition according to claim 10, wherein said nonionic
thickening polymers are chosen from polyether-polyurethanes
comprising at least two lipophilic hydrocarbon chains, comprising
from 6 to 30 carbon atoms, separated by a hydrophilic sequence,
wherein said hydrocarbon chains are chosen from pendant chains and
chains at the end of a hydrophilic sequence.
25. A composition according to claim 10, wherein said nonionic
thickening polymers are chosen from polyether-polyurethanes
comprising a polyblock sequence.
26. A composition according to claim 25, wherein said
polyether-polyurethanes are in tri-block form.
27. A composition according to claim 10, wherein said cationic
thickening polymers comprising at least one fatty chain are chosen
from quaternized cellulose derivatives and polyacrylates comprising
noncyclic amine-containing side groups.
28. A composition according to claim 1, wherein said at least one
thickening polymer comprising at least one fatty chain is present
in an amount ranging from 0.01% to 10% by weight relative to the
total weight of the composition.
29. A composition according to claim 28, wherein said at least one
thickening polymer comprising at least one fatty chain is present
in an amount ranging from 0.1% to 5% by weight relative to the
total weight of the composition.
30. A composition according to claim 1, wherein said at least one
oxidation dye is chosen from oxidation bases, oxidation couplers,
and their acid addition salts.
31. A composition according to claim 1, wherein said at least one
oxidation dye is chosen from oxidation bases.
32. A composition according to claim 31, wherein said oxidation
bases are chosen from ortho- and para-phenylenediamines, double
bases, ortho- and para-aminophenols, heterocyclic bases, and acid
addition salts of any of the foregoing.
33. A composition according to claim 32, wherein said
para-phenylenediamines are chosen from compounds of formula (I):
23wherein: R.sub.1 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl
groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, phenyl
groups, 4'-aminophenyl groups, and C.sub.1-C.sub.4 alkyl groups
substituted with at least one group chosen from nitrogen-containing
groups, R.sub.2 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl
groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, and
C.sub.1-C.sub.4 alkyl groups substituted with a nitrogen-containing
group; R.sub.1 and R.sub.2 may also form, together with the
nitrogen atom to which they are bonded, a 5- or 6-membered
nitrogen-containing heterocycle ring, optionally substituted with
at least one group chosen from alkyl groups, hydroxyl groups and
ureido groups; R.sub.3 is chosen from hydrogen, halogens,
C.sub.1-C.sub.4 alkyl groups, sulfo groups, carboxyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, hydroxy(C.sub.1-C.sub.4
alkyoxy) groups, acetylamino(C.sub.1-C.sub.4 alkoxy) groups,
mesylamino(C.sub.1-C.sub.4 alkoxy) groups, and
carbamoylamino(C.sub.1-C.sub.4 alkoxy) groups; and R.sub.4 is
chosen from hydrogen, halogens, and C.sub.1-C.sub.4 alkyl
groups.
34. A composition according to claim 33, wherein said R.sub.3 is
chlorine.
35. A composition according to claim 32, wherein said double bases
are chosen from compounds of formula (II): 24wherein: Z.sub.1 and
Z.sub.2, which may be identical or different, are each chosen from
hydroxyl groups, and --NH.sub.2 groups, optionally substituted with
a group chosen from C.sub.1-C.sub.4 alkyl groups, and linkers Y;
linker Y is chosen from linear and branched, divalent alkylene
groups comprising from 1 to 14 carbon atoms, optionally interrupted
by, or optionally terminating with, at least one entity chosen from
nitrogen-containing groups and heteroatoms, and optionally
substituted with at least one group chosen from hydroxyl groups,
and C.sub.1-C.sub.6 alkoxy groups; R.sub.5 and R.sub.6, which may
be identical or different, are each chosen from hydrogen, halogens,
C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.s- ub.4 alkyl)
groups, polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
amino(C.sub.1-C.sub.4 alkyl) groups, and linkers Y; and R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12, which may be
identical or different, are each chosen from hydrogen, linkers Y,
and C.sub.1-C.sub.4 alkyl groups; provided that said compounds of
formula (II) comprise only one linker Y per molecule.
36. A composition according to claim 35, wherein said heteroatoms
are chosen from oxygen, sulfur, and nitrogen.
37. A composition according to claim 33, wherein said
nitrogen-containing groups are chosen from amino,
mono(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)dialkylamino,
(C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium, and ammonium
radicals.
38. A composition according to claim 35, wherein said
nitrogen-containing groups are chosen from amino,
mono(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)dialkylamino,
(C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium, and ammonium
radicals.
39. A composition according to claim 32, wherein said
para-aminophenols are chosen from compounds of formula (III):
25wherein: R.sub.13 is chosen from hydrogen, halogens,
C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.sub.4 alkyl)
groups, (C.sub.1-C.sub.4)alkoxy(C.sub.- 1-C.sub.4)alkyl groups,
amino(C.sub.1-C.sub.4 alkyl), and
hydroxy(C.sub.1-C.sub.4)alkylamino(C.sub.1-C.sub.4 alkyl) groups;
and R.sub.14 is chosen from hydrogen, halogens, C.sub.1-C.sub.4
alkyl groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups, amino(C.sub.1-C.sub.4
alkyl) groups, cyano(C.sub.1-C.sub.4 alkyl) groups, and
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups.
40. A composition according to claim 39, wherein said halogens are
fluorine.
41. A composition according to claim 32, wherein said heterocyclic
bases are chosen from pyridine derivatives, pyrimidine derivatives,
pyrazolopyrimidine derivatives, and pyrazole derivatives.
42. A composition according to claim 31, wherein said oxidation
bases are present in an amount ranging from 0.0005% to 12% by
weight relative to the total weight of the composition.
43. A composition according to claim 30, wherein said oxidation
couplers are chosen from meta-phenylenediamines, meta-aminophenols,
meta-diphenols, heterocyclic couplers, and their acid addition
salts.
44. A composition according to claim 30, wherein said oxidation
couplers are present in an amount ranging from 0.0001% to 10% by
weight relative to the total weight of the composition.
45. A composition according to claim 30, wherein said acid addition
salts are chosen from hydrochlorides, hydrobromides, sulfates,
tartrates, lactates, and acetates.
46. A composition according to claim 1 further comprising at least
one direct dye.
47. A composition according to claim 1 further comprising at least
one reducing agent.
48. A composition according to claim 47, wherein said at least one
reducing agent is present in an amount ranging from 0.05% to 3% by
weight relative to the total weight of the composition.
49. A composition according to claim 1 further comprising at least
one fatty alcohol.
50. A composition according to claim 49, wherein said at least one
fatty alcohol is present in an amount ranging from 0.001% to 20% by
weight relative to the total weight of the composition.
51. A ready-to-use cosmetic composition for oxidation dyeing
keratin fibers, wherein said ready-to-use cosmetic composition is
obtained by combining at least one composition (A), in a dyeing
medium, comprising: at least one oxidation dye, at least one
thickening polymer comprising at least one fatty chain, and at
least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, with at least one composition (B)
comprising at least one oxidizing agent.
52. A composition according to claim 51, wherein said at least one
oxidizing agent is chosen from hydrogen peroxide, urea peroxide,
alkali metal bromates, alkali metal ferricyanides, persalts, and
oxidation-reduction enzymes.
53. A composition according to claim 52, wherein said
oxidation-reduction enzymes are chosen from laccases, peroxidases,
and oxidoreductases comprising 2 electrons.
54. A composition according to claim 52, wherein said at least one
oxidizing agent is hydrogen peroxide.
55. A composition according to claim 54, wherein said hydrogen
peroxide is present in an oxygenated water solution comprising a
titre ranging from 1 to 40 in volume.
56. A composition according to claim 1, wherein said composition
possesses a pH ranging from 4 to 12.
57. A composition according to claim 51, wherein said keratin
fibers are chosen from human keratin fibers.
58. A composition according to claim 57, wherein said human keratin
fibers are chosen from human hair.
59. A cosmetic composition according to claim 51 further comprising
at least one polymer chosen from cationic polymers and amphoteric
polymers, wherein said at least one polymer is present in said at
least one composition (A), in said at least one composition (B), or
in said at least one composition (A) and said at least one
composition (B).
60. A composition according to claim 59, wherein said at least one
polymer is chosen from cationic polymers chosen from quaternary
polyammoniums comprising recurring units of formula (W): 26
61. A composition according to claim 59, wherein said at least one
polymer is chosen from cationic polymers chosen from quaternary
polyammoniums comprising recurring units of formula (U): 27
62. A composition according to claim 59, wherein said at least one
polymer is chosen from amphoteric polymers chosen from copolymers
comprising at least one monomeric residue chosen from acrylic acid
residue and a residue of a salt of dimethyldiallylammonium.
63. A composition according to claim 59, wherein said at least one
polymer chosen from cationic polymers and amphoteric polymers is
present in an amount ranging from 0.01% to 10% by weight relative
to the total weight of the composition.
64. A composition according to claim 63, wherein said at least one
polymer chosen from cationic polymers and amphoteric polymers is
present in an amount ranging from 0.05% to 5% by weight relative to
the total weight of the composition.
65. A composition according to claim 64, wherein said at least one
polymer chosen from cationic polymers and amphoteric polymers is
present in an amount ranging from 0.1% to 3% by weight relative to
the total weight of the composition.
66. A composition according to claim 51 further comprising at least
one surfactant chosen from anionic, cationic, nonionic and
amphoteric surfactants, wherein said at least one surfactant is
present in said at least one composition (A), in said at least one
composition (B), or in said at least one composition (A) and said
at least one compostion (B).
67. A composition according to claim 10, wherein said anionic
thickening polymers are chosen from copolymers formed from at least
three monomers, wherein at least one of said at least three
monomers is chosen from a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation, at least one of said at
least three monomers is chosen from an ester of a carboxylic acid
with .alpha.,.beta.-monoethylenic unsaturation, and at least one of
said at least three monomers is chosen from an oxyalkylenated fatty
alcohol.
68. A composition according to claim 66, wherein said at least one
surfactant is present in an amount ranging from 0.01% to 40% by
weight relative to the total weight of the composition.
69. A composition according to claim 68, wherein said at least one
surfactant is present in an amount ranging from 0.1% to 30% by
weight relative to the total weight of the composition.
70. A composition according to claim 51 further comprising at least
one thickening agent chosen from cellulose derivatives, guar
derivatives, gums of microbial origin, and synthetic thickeners
which do not possess a fatty chain, wherein said at least one
thickening agent is present in said at least one composition (A),
in said at least one composition (B), or in said at least one
composition (A) and said at least one composition (B).
71. A composition according to claim 70, wherein said at least one
thickening agent is present in an amount ranging from 0.01% to 10%
by weight relative to the total weight of the composition.
72. A method for oxidation dyeing keratin fibers comprising: (a)
applying to said keratin fibers at least one composition (A)
comprising, in a dyeing medium: at least one oxidation dye, at
least one thickening polymer comprising at least one fatty chain,
and at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols; and (b) developing the color with
the aid of at least one oxidizing composition (B) comprising at
least one oxidizing agent, wherein said at least one oxidizing
composition (B) is combined at the time of use with said at least
one composition (A) or said at least one oxidizing composition (B)
is applied sequentially to said at least one composition (A)
without intermediate rinsing.
73. A method according to claim 72, wherein said keratin fibers are
chosen from human keratin fibers.
74. A method according to claim 73, wherein said human keratin
fibers are human hair.
75. A method for oxidation dyeing keratin fibers comprising:
applying to said keratin fibers at least one cosmetic dyeing
composition comprising, in a dyeing medium, at least one oxidation
dye and at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, and optionally comprising at least
one thickening polymer comprising at least one fatty chain,
developing the color with the aid of at least one oxidizing
composition comprising at least one oxidizing agent and an
effective quantity of at least one thickening polymer comprising at
least one fatty chain, wherein said at least one oxidizing
composition is combined at the time of use with said at least one
dyeing composition or wherein said at least one oxidizing
composition is applied sequentially to said at least one dyeing
composition without intermediate rinsing.
76. A method according to claim 75, wherein said keratin fibers are
chosen from human keratin fibers.
77. A method according to claim 76, wherein said human keratin
fibers are human hair.
78. A kit for dyeing keratin fibers comprising at least two
compartments wherein: a first compartment comprises (1) at least
one oxidation dye, (2) at least one thickening polymer comprising
at least one fatty chain, and (3) at least one fatty alcohol chosen
from monoglycerolated and polyglycerolated fatty alcohols, and a
second compartment comprises at least one oxidizing agent.
79. A kit according to claim 78, wherein said keratin fibers are
chosen from human keratin fibers.
80. A kit according to claim 79, wherein said human keratin fibers
are human hair.
81. A kit for dyeing keratin fibers comprising at least two
compartments wherein: a first compartment comprises at least one
oxidation dye and at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols, and
optionally comprises at least one thickening polymer comprising at
least one fatty chain and a second compartment comprises at least
one oxidizing agent and an effective quantity of at least one
thickening polymer comprising at least one fatty chain.
82. A kit according to claim 81, wherein said keratin fibers are
chosen from human keratin fibers.
83. A kit according to claim 82, wherein said human keratin fibers
are human hair.
84. A kit for dyeing keratin fibers comprising at least three
compartments wherein: a first compartment comprises at least one
oxidation dye and at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols, and
optionally comprises at least one thickening polymer comprising at
least one fatty chain, a second compartment comprises at least one
thickening polymer comprising at least one fatty chain and a third
compartment comprises at least one oxidizing agent and optionally
comprises at least one thickening polymer comprising at least one
fatty chain.
85. A kit according to claim 84, wherein said keratin fibers are
chosen from human keratin fibers.
86. A kit according to claim 85, wherein said human keratin fibers
are human hair.
87. A composition according to claim 23, wherein said hydrophilic
sequences are chosen from hydrophilic sequences of a
polyoxyethylenated nature and wherein said hydrophobic sequences
are chains chosen from aliphatic chains, cycloaliphatic chains, and
aromatic chains.
88. A composition according to claim 49, wherein said at least one
fatty alcohol is chosen from linear and branched, saturated and
unsaturated fatty alcohols.
Description
[0001] The present invention relates to cosmetic compositions for
oxidation dyeing of keratin fibers, such as human keratin fibers
like hair, comprising, in a dyeing medium, (1) at least one
oxidation dye, (2) at least one thickening polymer comprising at
least one fatty chain, and (3) at least one fatty alcohol chosen
from monoglycerolated and polyglycerolated fatty alcohols.
[0002] It is known to dye keratin fibers, for example human hair,
with dyeing compositions comprising oxidation dye precursors,
generally called "oxidation bases." Representative oxidation bases
include ortho- and para-phenylenediamines, ortho- and
para-aminophenols, and heterocyclic bases.
[0003] Oxidation dye precursors are compounds initially only
slightly colored or not colored that develop their dyeing power in
the hair in the presence of oxidizing agents, leading to the
formation of colored compounds. The formation of these colored
compounds results either from oxidative condensation of the
"oxidation bases" with themselves, or oxidative condensation of the
"oxidation bases" with color-modifying compounds, or "couplers,"
which are generally present in the dyeing compositions used in
oxidation dyeing. Representative couplers include
meta-phenylenediamines, meta-aminophenols, meta-diphenols, and
certain heterocyclic compounds.
[0004] The variety of compositions that can be employed in
oxidation coloration, chosen from oxidation bases, oxidation
couplers and mixtures of oxidation bases and couplers, can
contribute to a pallet very rich in color.
[0005] Traditional thickeners, which can provide a gelling effect
when diluted by water and/or surfactants, have been used
conventionally to localize the dye product as applied on hair, so
that the dye product does not touch the face or the area outside
the area to be dyed. Such thickeners, chosen as appropriate, for
example include crosslinked polyacrylic acid,
hydroxyethylcelluloses, certain polyurethanes, waxes or mixtures of
nonionic surfactants having an HLB (Hydrophilic Lipophilic
Balance).
[0006] However, the inventors have observed that the
above-mentioned thickening systems may impede a result of intense
and chromatic shades of low selectivity and good fastness and a
good cosmetic condition to the treated hair. However, it has also
been observed that the ready-to-use dyeing compositions comprising
known oxidation dye(s) and thickening systems tend to result in
imprecise application of such compositions and/or a decrease in
viscosity over time.
[0007] The inventors have discovered that it is possible to obtain
ready-to-use oxidation dyeing compositions that resist running and
tend to remain well-confined to the site of application.
Additionally, such compositions may favor more intense and more
chromatic (radiant) shades, while exhibiting low selectivities and
good fastness toward chemical agents (shampoo, permanent waving and
the like) and/or natural agents (light, perspiration and the like),
and while offering the hair good cosmetic properties. The inventors
have discovered that it is possible to obtain at least one of the
aforementioned characteristics by formulating a ready-to-use
cosmetic dyeing composition comprising (1) at least one oxidation
dye, (2) at least one thickening polymer comprising at least one
fatty chain, and (3) at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols.
[0008] The inventors have discovered that it is possible to obtain
at least one of the aforementioned characteristics by formulating a
ready-to-use cosmetic dyeing composition comprising (1) at least
one oxidation dye, (2) at least one thickening polymer comprising
at least one fatty chain, and (3) at least one fatty alcohol chosen
from monoglycerolated and polyglycerolated fatty alcohols.
[0009] The inventors have also discovered that said compositions
comprising (1) at least one oxidation dye, (2) at least one
thickening polymer comprising at least one fatty chain, and (3) at
least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols tend to be stable upon storage.
[0010] At least one of these discoveries forms the basis of the
present invention.
[0011] One subject of the present invention is thus a cosmetic
composition for oxidation dyeing keratin fibers, such as human
keratin fibers like hair, comprising, in a dyeing medium (1) at
least one oxidation dye, (2) at least one thickening polymer
comprising at least one fatty chain, and (3) at least one fatty
alcohol chosen from monoglycerolated and polyglycerolated fatty
alcohols.
[0012] Another subject of the invention relates to a ready-to-use
cosmetic composition for oxidation dyeing keratin fibers
comprising, in a dyeing medium, (1) at least one oxidation dye, (2)
at least one thickening polymer comprising at least one fatty
chain, (3) at least one fatty alcohol chosen from monoglycerolated
and polyglycerolated fatty alcohols, and (4) at least one oxidizing
agent. The term "ready-to-use composition" is understood to mean,
for the purposes of the present invention, a composition intended
to be applied immediately to the keratin fibers, either stored as
it is before use or obtained from the mixture of two or more
compositions.
[0013] The invention also relates to a method for oxidation dyeing
keratin fibers, such as human keratin fibers like hair, comprising
applying to said keratin fibers at least one composition (A)
comprising, in a dyeing medium:
[0014] at least one oxidation dye,
[0015] at least one thickening polymer comprising at least one
fatty chain, and
[0016] at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, developing the color with the aid
of at least one composition (B) comprising at least one oxidizing
agent, wherein said at least one oxidizing composition (B) is
combined at the time of use with said at least one composition (A)
or said at least one oxidizing composition (B) is applied
sequentially to said at least one composition (A) without
intermediate rinsing.
[0017] A variation of the above-described method is a method for
oxidation dyeing keratin fibers, such as human keratin fibers like
hair, comprising:
[0018] applying to said keratin fibers at least one dyeing
composition comprising, in a dyeing medium, at least one oxidation
dye and at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, and optionally comprising at least
one thickening polymer comprising at least one fatty chain,
[0019] developing the color with the aid of at least one oxidizing
composition comprising at least one oxidizing agent and an
effective quantity of at least one thickening polymer comprising at
least one fatty chain,
[0020] wherein said at least one oxidizing composition is combined
at the time of use with said at least one dyeing composition or
wherein said at least one oxidizing composition is applied
sequentially to said at least one dyeing composition without
intermediate rinsing.
[0021] One embodiment of the invention relates to multicompartment
dyeing devices or "kits" for oxidation dyeing keratin fibers, such
as human keratin fibers like hair.
[0022] A kit according to the invention comprises at least two
compartments, wherein:
[0023] a first compartment comprises (1) at least one oxidation
dye, (2) at least one thickening polymer comprising at least one
fatty chain, and (3) at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols, and
[0024] a second compartment comprises at least one oxidizing
agent.
[0025] According to one variant, another kit comprises at least two
compartments, wherein:
[0026] a first compartment comprises at least one oxidation dye and
at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, and optionally comprises at least
one thickening polymer comprising at least one fatty chain and
[0027] a second compartment comprises at least one oxidizing agent
and an effective quantity of at least one thickening polymer
comprising at least one fatty chain.
[0028] According to another variant, a three-compartment kit
comprises:
[0029] a first compartment comprising at least one oxidation dye
and at least one fatty alcohol chosen from monoglycerolated and
polyglycerolated fatty alcohols, and optionally comprising at least
one thickening polymer comprising at least one fatty chain,
[0030] a second compartment comprising at least one thickening
polymer comprising at least one fatty chain and
[0031] a third compartment comprising at least one oxidizing agent
and optionally comprising at least one thickening polymer
comprising at least one fatty chain.
[0032] At Least One Fatty Alcohol Chosen From Monoglycerolated and
Polyglycerolated Fatty Alcohols
[0033] The expression at least one (as used herein, "at least one"
means one or more and thus includes mixtures and combinations)
fatty alcohol chosen from monoglycerolated and polyglycerolated
fatty alcohols is understood to mean compounds of the following
formula:
RO--(--CH.sub.2--CH(CH.sub.2OH)--O--).sub.n--H
[0034] in which:
[0035] R is chosen from linear and branched, saturated and
unsaturated groups comprising from 8 to 40 carbon atoms, such as
from 10 to 30 carbon atoms;
[0036] n is a number ranging from 1 to 30, such as from 1 to
10.
[0037] Representative monoglycerolated and polyglycerolated fatty
alcohols include, for example, lauryl alcohol comprising 4 mol of
glycerol (INCI name: POLYGLYCERYL-4 LAURYL ETHER), oleyl alcohol
comprising 4 mol of glycerol (INCI name: POLYGLYCERYL-4 OLEYL
ETHER), oleyl alcohol comprising 2 mol of glycerol (INCI name:
POLYGLYCERYL-2 OLEYL ETHER), cetearyl alcohol comprising 2 mol of
glycerol, cetearyl alcohol comprising 6 mol of glycerol, oleocetyl
alcohol comprising 6 mol of glycerol and octadecanol comprising 6
mol of glycerol.
[0038] The fatty alcohol may represent a mixture of fatty alcohols
in the same way that the value of n represents a statistical value,
which means that in a commercial product, for example, several
species of polyglycerolated fatty alcohols can coexist in the form
of a mixture.
[0039] The at least one fatty alcohol chosen from monoglycerolated
and polyglycerolated fatty alcohols can be present in an amount
ranging for example from 0.01% to 30% by weight relative to the
total weight of the composition, such as from 0.05% to 20% by
weight relative to the total weight of the composition and further
such as from 0.1% to 15% by weight relative to the total weight of
the composition.
[0040] At Least One Thickening Polymer Comprising At Least One
Fatty Chain
[0041] The at least one thickening polymer comprising at least one
fatty chain according to the invention can be chosen from nonionic,
anionic and cationic thickening polymers comprising at least one
fatty chain.
[0042] (i) Anionic Thickeners
[0043] Such anionic thickening polymers comprising at least one
fatty chain can be chosen from:
[0044] (I) anionic polymers comprising at least one hydrophilic
unit and at least one allyl ether unit comprising at least one
fatty chain, for example said anionic polymers wherein said at
least one hydrophilic unit comprises at least one ethylenic
unsaturated anionic monomeric residue, such as vinylcarboxylic acid
and further such as at least one monomeric residue chosen from
acrylic acid and methacrylic acid residues, and wherein said at
least one allyl ether unit comprising at least one fatty chain
corresponds to the monomeric residue resulting from the monomer of
formula (I):
CH.sub.2.dbd.C--R'--CH.sub.2--O--B.sub.n--R (I)
[0045] in which R' is chosen from H and CH.sub.3, B is chosen from
ethyleneoxy groups, n is chosen from zero and integers ranging from
1 to 100, R is a hydrocarbon group chosen from alkyl, arylalkyl,
aryl, alkylaryl and cycloalkyl groups, comprising from 8 to 30
carbon atoms, such as from 10 to 24, and further such as from 12 to
18 carbon atoms. One embodiment of the invention comprises at least
one allyl ether unit of the monomeric resudue resulting from the
monomer of formula (I), wherein R' is H, n is equal to 10, and R is
a stearyl (C.sub.18) group.
[0046] Representative anionic amphiphilic polymers of this type are
described and prepared, according to a method of emulsion
polymerization, in patent EP-0,216,479, the disclosure of which is
incorporated by reference herein.
[0047] As used herein, the term "lower alkyl" means an alkyl chosen
from saturated and unsaturated, branched and unbranched
C.sub.1-C.sub.6 alkyl groups.
[0048] Representative anionic thickening polymers comprising at
least one fatty chain include for example polymers formed from 20%
to 60% by weight of at least one monomer chosen from acrylic acid
and methacrylic acid, 5% to 60% by weight of C.sub.1-C.sub.6
alkyl(meth)acrylates, 2% to 50% by weight of allyl ether comprising
at least one fatty chain of formula (I), and up to 1% by weight of
a crosslinking agent chosen from well known copolymerizable
polyethylenic unsaturated monomers such as diallyl phthalate, allyl
(meth)acrylate, divinylbenzene, (poly)ethylene glycol
dimethacrylate and methylenebisacrylamide.
[0049] One embodiment could comprise at least one anionic
thickening polymer chosen from crosslinked terpolymers of
methacrylic acid, ethyl acrylate, and polyethylene glycol (10 EO)
stearyl alcohol ether (Steareth 10), such as the products sold by
the company ALLIED COLLOIDS under the names SALCARE SC 80 and
SALCARE SC 90, which are aqueous emulsions comprising 30% of a
crosslinked terpolymer of methacrylic acid, of ethyl acrylate and
of steareth-10-allyl ether (40/50/10).
[0050] Anionic thickening polymers comprising at least one fatty
chain can also be chosen from:
[0051] (II) anionic polymers comprising at least one hydrophilic
unit of the olefinic unsaturated carboxylic acid type and at least
one hydrophobic unit of the (C.sub.10-C.sub.30)alkyl ester of
unsaturated carboxylic acid type.
[0052] Such polymers are chosen from polymers comprising:
[0053] at least one hydrophilic unit formed from olefinic
unsaturated carboxylic acid monomers of formula (II): 1
[0054] in which R.sub.1 is chosen from H, CH.sub.3, and
C.sub.2H.sub.5, (which corresponds with acrylic acid, methacrylic
acid and ethacrylic acid units), and
[0055] at least one hydrophobic unit formed from
(C.sub.10-C.sub.30)alkyl esters of unsaturated carboxylic acid
monomers of formula (III): 2
[0056] in which R.sub.2 is chosen from H, CH.sub.3, and
C.sub.2H.sub.5, (which corresponds with acrylate, methacrylate and
ethacrylate units) and R.sub.3 is chosen from saturated and
unsaturated, branched and unbranched C.sub.10-C.sub.30 alkyl
groups. In one embodiment, for example, R.sub.2 is chosen from H
(acrylate units) and CH.sub.3 (methacrylate units) and R.sub.3 is
chosen from C.sub.12-C.sub.22 alkyl groups.
[0057] (C.sub.10-C.sub.30)alkyl esters of unsaturated carboxylic
acids in accordance with the invention include for example lauryl
acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate,
dodecyl acrylate, lauryl methacrylate, stearyl methacrylate, decyl
methacrylate, isodecyl methacrylate, and dodecyl methacrylate.
[0058] Anionic polymers of this type are for example described and
prepared according to U.S. Pat. Nos. 3,915,921 and 4,509,949, the
disclosures of which are incorporated by reference herein.
[0059] Anionic thickening polymers comprising at least one fatty
chain that can be used include polymers formed from a mixture of
monomers comprising:
[0060] (i) acrylic acid,
[0061] (ii) at least one ester of formula (III) described above
wherein R.sub.2 is chosen from H and CH.sub.3, and R.sub.3 is
chosen from alkyl groups comprising from 12 to 22 carbon atoms,
and
[0062] (iii) at least one crosslinking agent chosen from well known
copolymerizable polyethylenic unsaturated monomers such as diallyl
phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene
glycol dimethacrylate and methylenebisacrylamide.
[0063] Representative anionic thickening polymers comprising at
least one fatty chain that can be used include (i) polymers
comprising 95% to 60% by weight of acrylic acid monomeric residue
(hydrophilic unit), 4% to 40% by weight of C.sub.10-C.sub.30 alkyl
acrylate monomeric residue (hydrophobic unit), and 0% to 6% by
weight of crosslinking polymerizable monomeric residue, and (ii)
polymers comprising 98% to 96% by weight of acrylic acid monomeric
residue (hydrophilic unit), 1% to 4% by weight of C.sub.10-C.sub.30
alkyl acrylate monomeric residue (hydrophobic unit) and 0.1% to
0.6% by weight of crosslinking polymerizable monomeric residue such
as those described above.
[0064] Among the above polymers, the products sold by the company
GOODRICH under the trade names PEMULEN TR1, PEMULEN TR2, and
CARBOPOL 1382 can be used. One embodiment could employ at least one
polymer chosen from PEMULEN TR1, and the product sold by the
company S.E.P.P.I.C. under the name COATEX SX.
[0065] Anionic thickening polymers comprising at least one fatty
chain can also be chosen from:
[0066] (III) terpolymers formed from maleic
anhydride/C.sub.30-C.sub.38 .alpha.-olefin/alkyl maleate such as
the product (maleic anhydride/C.sub.30-C.sub.38
.alpha.-olefin/isopropyl maleate copolymer) sold under the name
PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES,
[0067] (IV) acrylic terpolymers formed from:
[0068] (a) 20% to 70% by weight of a carboxylic acid with
.alpha.,.beta.-monoethylenic unsaturation
[0069] (b) 20% to 80% by weight of a nonsurfactant monomer with
.alpha.,.beta.-monoethylenic unsaturation different from (a)
[0070] (c) 0.5% to 60% by weight of a nonionic monourethane which
is the product of the reaction of a monohydric surfactant with a
monoisocyanate with monoethylenic unsaturation
[0071] such as acrylic terpolymers described in patent application
EP-A-0,173,109, the disclosure of which is incorporated by
reference herein, and more particularly acrylic terpolymers
described therein in Example 3, namely a methacrylic acid/methyl
acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated
(40 EO) behenyl alcohol terpolymer in 25% aqueous dispersion,
[0072] (V) copolymers formed from at least two monomers, wherein at
least one of said at least two monomers is chosen from a carboxylic
acid with .alpha.,.beta.-monoethylenic unsaturation, an ester of a
carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation, and
an oxyalkylenated fatty alcohol, and
[0073] (VI) copolymers formed from at least three monomers, wherein
at least one of said at least three monomers is chosen from a
carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation, at
least one of said at least three monomers is chosen from an ester
of a carboxylic acid with .alpha.,.beta.-monoethylenic unsaturation
and at least one of said at least three monomers is chosen from an
oxyalkylenated fatty alcohol.
[0074] Additionally, these compounds can also comprise, as monomer,
a carboxylic acid ester comprising an .alpha.,.beta.-monoethylenic
unsaturation and a C.sub.1-C.sub.4 alcohol. By way of example of
this type of compound, there may be mentioned ACULYN 22 sold by the
company ROHM and HAAS, which is an oxyalkylenated stearyl
methacrylate/ethyl acrylate/methacrylic acid terpolymer.
[0075] (ii) Nonionic Thickeners
[0076] Nonionic thickening polymers comprising at least one fatty
chain according to the invention can be chosen from:
[0077] (1) celluloses modified by at least one group comprising at
least one fatty chain such as:
[0078] hydroxyethylcelluloses modified by at least one group
comprising at least one fatty chain such as alkyl, arylalkyl and
alkylaryl groups and further such as alkyl, arylalkyl and alkylaryl
groups wherein said alkyl groups comprise from 8-22 carbon atoms,
such as the product NATROSOL PLUS GRADE 330 CS (C.sub.16 alkyls)
sold by the company AQUALON, and the product BERMOCOLL EHM 100 sold
by the company BEROL NOBEL,
[0079] hydroxyethylcelluloses modified by at least one polyalkylene
glycol ether of alkylphenol group, such as the product AMERCELL
POLYMER HM-1500 (polyethylene glycol (15) ether of nonylphenol)
sold by the company AMERCHOL;
[0080] (2) hydroxypropylguars modified by at least one group
comprising at least one fatty chain such as the product ESAFLOR HM
22 (C.sub.22 alkyl chain) sold by the company LAMBERTI, the
products RE 210-18 (C.sub.14 alkyl chain) and RE 205-1 (C.sub.20
alkyl chain) sold by the company RHONE POULENC (Succeeded by RHODIA
CHIMIE);
[0081] (3) copolymers formed from vinylpyrrolidone and at least one
hydrophobic monomer comprising at least one fatty chain such as for
example:
[0082] the products ANTARON V216 and GANEX V216
(vinylpyrrolidone/hexadece- ne copolymer) sold by the company
I.S.P., and
[0083] the products ANTARON V220 and GANEX V220
(vinylpyrrolidone/eicosene copolymer) sold by the company
I.S.P.;
[0084] (4) copolymers formed from at least one C.sub.1-C.sub.6
alkyl methacrylate and at least one amphiphilic monomer comprising
at least one fatty chain and copolymers formed from at least one
C.sub.1-C.sub.6 alkyl acrylate and at least one amphiphilic monomer
comprising at least one fatty chain such as for example the
oxyethylenated stearyl acrylate/methyl acrylate copolymer sold by
the company GOLDSCHMIDT under the name ANTIL 208;
[0085] (5) copolymers formed from at least one hydrophilic
methacrylate and at least one hydrophobic monomer comprising at
least one fatty chain and copolymers formed from at least one
hydrophilic acrylate and at least one hydrophobic monomer
comprising at least one fatty chain such as for example the
polyethylene glycol methacrylate/lauryl methacrylate copolymer;
[0086] (6) polyether-polyurethanes comprising in their chain both
hydrophilic sequences which are most often of a polyoxyethylenated
nature and hydrophobic sequences which may be chains chosen from
aliphatic chains, cycloaliphatic chains, and aromatic chains;
[0087] (7) polymers comprising an aminoplast ether backbone
possessing at least one fatty chain, such as the compounds PURE
THIX provided by the company SUD-CHEMIE.
[0088] Nonionic thickening polymers can additionally include
polyether-polyurethanes comprising at least two lipophilic (i.e.,
hydrophobic) hydrocarbon chains, comprising from 6 to 30 carbon
atoms, separated by a hydrophilic sequence, it being possible for
the hydrocarbon chains to be chosen from pendant chains and chains
at the end of a hydrophilic sequence. One embodiment may comprise
at least one pendant chain. In addition, the polymer may comprise a
hydrocarbon chain at at least one end of a hydrophilic
sequence.
[0089] Representative polyether-polyurethanes useful in the present
invention may be polyblocks, such as in triblock form. The
hydrophobic sequences may be at each end of the chain (for example:
triblock copolymer with hydrophilic central sequence) and
optionally both at the ends and in the chain (polyblock copolymer
for example). These same polymers may also be in the form of graft
units or may be star-shaped.
[0090] The nonionic polyether-polyurethanes comprising at least one
fatty chain may be triblock copolymers whose hydrophilic sequence
is a polyoxyethylenated chain comprising from 50 to 1000
oxyethylenated groups. Certain nonionic polyether-polyurethanes
comprise a urethane bond between the hydrophilic sequences.
[0091] By extension, those whose hydrophilic sequences are linked
by other chemical bonds to the lipophilic sequences are also
included among the nonionic polyether-polyurethanes comprising at
least one fatty chain.
[0092] Representative nonionic polyether-polyurethanes comprising
at least one fatty chain include Rholate 205 comprising a urea
function sold by the company RHEOX and Rholate 208, 204 and 212, as
well as Acrysol RM 184, Aculyn 44 and Aculyn 46 from the company
ROHM and HAAS [ACULYN 46 is a polycondensate of polyethylene glycol
comprising 150 or 180 mol of ethylene oxide, stearyl alcohol and
methylene-bis(4-cyclohexylisocyanate) (SMDI), at 15% by weight in a
maltodextrin (4%) and water (81%) matrix; ACULYN 44 is a
polycondensate of polyethylene glycol comprising 150 or 180 mol of
ethylene oxide, decyl alcohol and methylenebis(4-cyclohexyliso-
cyanate) (SMDI), at 35% by weight in a propylene glycol (39%) and
water (26%) mixture].
[0093] There may also be mentioned the product ELFACOS T210
comprising a C.sub.12-C.sub.14 alkyl chain and the product ELFACOS
T212 comprising a C.sub.18 alkyl chain from AKZO.
[0094] The product DW 1206B from RHOM & HAAS comprising a
C.sub.20 alkyl chain and with a urethane bond, sold at 20% dry
matter content in water, may also be used.
[0095] It is also possible to use solutions and dispersions of
these polymers for example in water and for example in an
aqueous-alcoholic medium. By way of example of such polymers, there
may be mentioned Rholate 255, Rholate 278 and Rholate 244 sold by
the company RHEOX. It is also possible to use the product DW 1206F
and DW 1206J provided by the company ROHM & HAAS.
[0096] Representative polyether-polyurethanes that can be used
according to the invention include polyether-polyurethanes
described in the article by G. Fonnum, J. Bakke and Fk.
Hansen--Colloid Polym. Sci 271, 380, 389 (1993), the disclosure of
which is incorporated by reference herein.
[0097] (iii) Cationic Thickeners
[0098] As used herein, "cationic thickener" refers to polymers
chosen from polymers comprising at least one cationic group and
polymers comprising at least one group which can be ionized to form
cationic groups.
[0099] Representative cationic thickening polymers comprising at
least one fatty chain used in the present invention can be chosen
from quaternized cellulose derivatives and polyacrylates with
noncyclic amine-containing side groups.
[0100] Such quaternized cellulose derivatives can be chosen
from:
[0101] quaternized celluloses modified by groups comprising at
least one fatty chain, such as at least one group chosen from
alkyl, arylalkyl and alkylaryl groups comprising at least 8 carbon
atoms,
[0102] quaternized hydroxyethylcelluloses modified by at least one
group comprising at least one fatty chain, such as at least one
group chosen from alkyl, arylalkyl and alkylaryl groups comprising
at least 8 carbon atoms.
[0103] In one embodiment, said alkyl groups carried by the above
quaternized celluloses and hydroxyethylcelluloses comprise from 8
to 30 carbon atoms and the aryl groups are chosen from phenyl,
benzyl, naphthyl and anthryl groups.
[0104] There may be mentioned as examples of quaternized
alkylhydroxyethylcelluloses comprising at least one
C.sub.8-C.sub.30 fatty chain the products QUATRISOFT LM 200,
QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C.sub.12 alkyl)
and QUATRISOFT LM-X 529-8 (C.sub.18 alkyl) marketed by the company
AMERCHOL and the products CRODACEL QM, CRODACEL QL (C.sub.12 alkyl)
and CRODACEL QS (C.sub.18 alkyl) marketed by the company CRODA.
[0105] Representative polyacrylates with amine-containing side
groups, quaternized and otherwise, comprise for example hydrophobic
groups of the steareth 20 type (polyoxyethylenated stearyl alcohol
(20)).
[0106] As examples of polyacrylates with amine-containing side
groups, there may be mentioned the polymers 8781-121B or 9492-103
from the company NATIONAL STARCH.
[0107] One embodiment of the oxidation dyeing composition according
to the invention may comprise at least one nonionic thickening
polymer comprising at least one fatty chain.
[0108] The anionic, nonionic and cationic at least one thickening
polymer comprising at least one fatty chain is generally present in
an amount ranging for example from 0.01% to 10% by weight relative
to the total weight of the dyeing composition, such as from 0.1% to
5% by weight relative to the total weight of the dyeing
composition.
[0109] Oxidation Dyes
[0110] The at least one oxidation dye which can be used according
to the present invention is chosen from oxidation bases, and
oxidation couplers. In one embodiment, the compositions can
comprise at least one oxidation base.
[0111] The oxidation bases usable in the context of the present
invention are chosen from those conventionally known as oxidation
dyes. Representative oxidation dyes include ortho- and
para-phenylenediamines, double bases, ortho- and para-aminophenols
and heterocyclic bases as well as their addition salts with an
acid.
[0112] For example, the following oxidation bases may be used:
[0113] (I) para-phenylenediamines chosen from compounds of formula
(I), and their acid addition salts: 3
[0114] wherein:
[0115] R.sub.1 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl
groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, phenyl
groups, 4'-aminophenyl groups, and C.sub.1-C.sub.4 alkyl groups
substituted with at least one group chosen from nitrogen-containing
groups,
[0116] R.sub.2 is chosen from hydrogen, C.sub.1-C.sub.4 alkyl
groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl groups, and
C.sub.1-C.sub.4 alkyl groups substituted with a nitrogen-containing
group;
[0117] R.sub.1 and R.sub.2 may also form, together with the
nitrogen atom to which they are bonded, a 5- or 6-membered
nitrogen-containing heterocycle ring, optionally substituted with
at least one group chosen from alkyl groups, hydroxyl groups and
ureido groups;
[0118] R.sub.3 is chosen from hydrogen, halogens, such as chlorine,
C.sub.1-C.sub.4 alkyl groups, sulfo groups, carboxyl groups,
monohydroxy(C.sub.1-C.sub.4 alkyl) groups, hydroxy(C.sub.1-C.sub.4
alkyoxy) groups, acetylamino(C.sub.1-C.sub.4 alkoxy) groups,
mesylamino(C.sub.1-C.sub.4 alkoxy) groups, and
carbamoylamino(C.sub.1-C.s- ub.4 alkoxy) groups;
[0119] R.sub.4 is chosen from hydrogen, halogens, and
C.sub.1-C.sub.4 alkyl groups.
[0120] Suitable nitrogen-containing groups of formula (I) above
may, for example, be chosen from amino,(C.sub.1-C.sub.4)
monoalkylamino, (C.sub.1-C.sub.4)dialkylamino,
(C.sub.1-C.sub.4)trialkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium, and ammonium
groups.
[0121] Representative para-phenylenediamines of formula (I) above
which may be used include para-phenylenediamine,
para-tolylenediamine, 2-chloro-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-ph- enylenediamine,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-methylaniline,
4-N,N-bis(.beta.-hydroxyethyl)amino-2-chloroaniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N,N-(ethyl-.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine,
2-methyl-1-N-.beta.-hydrox- yethyl-para-phenylenediamine and their
acid addition salts.
[0122] In other embodiments of the present invention,
para-phenylenediamines of formula (I) above can, for example, be
chosen from para-phenylenediamine, para-tolylenediamine,
2-isopropyl-para-phenyl- enediamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenyle- nediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylened-
iamine, N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine, and their acid addition salts.
[0123] According to the invention, "double bases" is understood to
mean the compounds comprising at least two aromatic rings on which
at least one functional group chosen from amino groups and hydroxyl
groups are carried.
[0124] (II) double bases chosen from compounds comprising at least
two aromatic rings substituted with at least one group chosen from
amino and hydroxyl groups. Such double bases may be chosen from
compounds of formula (II), and their acid addition salts: 4
[0125] wherein:
[0126] Z.sub.1 and Z.sub.2, which may be identical or different,
are each chosen from hydroxyl groups, and --NH.sub.2 groups,
optionally substituted with a group chosen from C.sub.1-C.sub.4
alkyl groups, and linkers Y;
[0127] linker Y is chosen from linear and branched, divalent
alkylene groups comprising from 1 to 14 carbon atoms, optionally
interrupted by, or optionally terminating with, at least one entity
chosen from nitrogen-containing groups and heteroatoms such as
oxygen, sulfur, and nitrogen, and optionally substituted with at
least one group chosen from hydroxyl groups, and C.sub.1-C.sub.6
alkoxy groups;
[0128] R.sub.5 and R.sub.6, which may be identical or different,
are each chosen from hydrogen, halogens, C.sub.1-C.sub.4 alkyl
groups, monohydroxy(C.sub.1-C.sub.4 alkyl) groups,
polyhydroxy(C.sub.2-C.sub.4 alkyl) groups, amino(C.sub.1-C.sub.4
alkyl) groups, and linkers Y;
[0129] R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12,
which may be identical or different, are each chosen from hydrogen,
linkers Y, and C.sub.1-C.sub.4 alkyl groups;
[0130] provided that said compounds of formula (II) comprise only
one linker Y per molecule.
[0131] Suitable nitrogen-containing groups of formula (II) include
mono(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)dialkylamino,
(C,-C.sub.4)trialkylamino, monohydroxy(C.sub.1-C.sub.4)alkylamino,
imidazolinium and ammonium groups.
[0132] Representative double bases of formula (II) include
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropano-
l,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(.beta.-hydroxyethy-
l)-N,N'-bis(4-aminophenyl)tetramethylenediamine,
N,N'-bis(4-methylaminophe- nyl)tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphen-
yl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane,
and their acid addition salts.
[0133] In another embodiment of the invention, the double bases of
formula (II) may be chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminoph-
enyl)-1,3-diaminopropanol,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their acid
addition salts.
[0134] (III) para-aminophenols chosen from compounds of formula
(III), and their acid addition salts: 5
[0135] wherein:
[0136] R.sub.13 is chosen from hydrogen, halogens, such as
fluorine, C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.sub.4
alkyl) groups, (C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl
groups, amino(C.sub.1-C.sub.4 alkyl), and
hydroxy(C.sub.1-C.sub.4)alkylamino(C.su- b.1-C.sub.4 alkyl)
groups;
[0137] R.sub.14 is chosen from hydrogen, halogens, such as
fluorine, C.sub.1-C.sub.4 alkyl groups, monohydroxy(C.sub.1-C.sub.4
alkyl) groups, polyhydroxy(C.sub.2-C.sub.4 alkyl) groups,
amino(C.sub.1-C.sub.4 alkyl) groups, cyano(C.sub.1-C.sub.4 alkyl)
groups, and (C.sub.1-C.sub.4)alkoxy(- C.sub.1-C.sub.4)alkyl
groups.
[0138] Representative para-aminophenols of formula (III) above
include para-aminophenol, 4-amino-3-methylphenol,
4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,
4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,
4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)ph- enol, and their acid
addition salts.
[0139] (IV) ortho-aminophenols chosen, for example, from
2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene,
2-amino-1-hydroxy-6-methylbenzene, 5-acetamido-2-aminophenol, and
their acid addition salts.
[0140] (V) heterocyclic bases chosen, for example, from pyridine
derivatives, pyrimidine derivatives, pyrazole derivatives,
pyrazolo-pyrimidine derivatives, and their acid addition salts.
[0141] Representative pyridine derivatives include
2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine,
2,3-diamino-6-methoxypyridine,
2-(.beta.-methoxyethyl)amino-3-amino-6-methoxypyridine,
3,4-diaminopyridine, and their acid addition salts. Some of the
aforementioned pyridine derivatives have been described, for
example in the patents GB 1,026,978 and GB 1,153,196, the
disclosures of which are incorporated by reference herein.
[0142] Representative pyrimidine derivatives include
2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and
their acid addition salts. Some of the aforementioned pyrimidine
derivatives have been described, for example in German Patent DE
2,359,399, Japanese Patents JP 88-169,571 and JP 91-10659, and
Patent Application WO 96/15765, the disclosures of which are
incorporated by reference herein.
[0143] Representative pyrazolo-pyrimidine derivatives include those
described, for example, in the patent application FR-A-2 750 048,
the disclosure of which is incorporated by reference herein. Such
pyrazolo-pyrimidine derivatives include pyrazolo[1,5-a]pyrimidines,
such as
[0144] pyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0145] 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0146] pyrazolo[1,5-a]pyrimidine-3,5-diamine;
[0147] 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;
[0148] 3-aminopyrazolo[1,5-a]pyrimidin-7-ol;
[0149] 3-aminopyrazolo[1,5-a]pyrimidin-5-ol ;
[0150] 2(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;
[0151] 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;
[0152]
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]eth-
anol;
[0153]
2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]eth-
anol;
[0154] 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0155] 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0156]
2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;
[0157]
3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine;
[0158] their salts, such as their acid addition salts, and their
tautomeric forms when a tautomeric equilibrium exists.
[0159] Representative pyrazole derivatives include
4,5-diamino-1-methylpyr- azole, 3,4-diaminopyrazole,
4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyrazole,
4-amino-1,3-dimethyl-5-hydrazinopy- razole,
1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-
-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxyethyl)pyrazole,
4,5-diamino-1-ethyl-3-methyl- pyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-- 1-methylpyrazole,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-methyl-1-isopropylpyrazole,
4-amino-5-(2'-aminoethyl)amino-- 1,3-dimethyl-pyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyra- zole,
3,5-diamino-1-methyl-4-methylaminopyrazole,
3,5-diamino-4-(.beta.-hy- droxyethyl)amino-1-methylpyrazole, and
their acid addition salts. Some of the aforementioned pyrazole
derivatives have been described, for example in Patents DE
3,843,892, DE 4,133,957 and Patent Applications WO 94/08969, WO
94/08970, FR-A-2,733,749 and DE 195 43 988, the disclosures of
which are incorporated by reference herein.
[0160] In accordance with the present invention, the oxidation
bases are generally present in an amount ranging for example from
0.0005% to 12% by weight relative to the total weight of the
composition, such as from 0.005% to 8% by weight relative to the
total weight of the composition.
[0161] Suitable couplers which may be used in the dyeing process of
the invention include couplers conventionally used in oxidation
dyeing compositions. Such couplers can be chosen, for example, from
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthols, sesamol and its derivatives, heterocyclic couplers, such
as, for example, indole derivatives, indoline derivatives, pyridine
derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles,
benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles,
quinolines and their acid addition salts.
[0162] Representative couplers include 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,
4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethyloxy)benz- ene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 6-hydroxyindole, 4-hydroxyindole,
4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1-H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one,
1-amino-2-methoxy-4,5-methylenedioxybenzene,
2-amino-3-hydroxypyridine,
3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,
2,6-dimethylpyrazolo[1,5-b]-1- ,2,4-triazole, and their acid
addition salts.
[0163] When these couplers are present, they are generally present
in an amount ranging for example from 0.0001% to 10% by weight
relative to the total weight of the composition, such as from
0.005% to 5% by weight relative to the total weight of the
composition.
[0164] Generally, the acid addition salts of the oxidation bases
and couplers can be chosen from hydrochlorides, hydrobromides,
sulfates, tartrates, lactates and acetates.
[0165] The compositions according to the invention may also
comprise at least one direct dye. Representative direct dyes which
can be used in the present invention include direct dyes that have
conventionally been used in direct dyeing compositions and lighting
direct dyeing compositions. For example, the dyes can be chosen
from neutral, cationic, and anionic nitro dyes, neutral, cationic,
and anionic anthraquinone dyes, and neutral, cationic, and anionic
azo dyes. Generally, the direct dyes are present in amounts ranging
for example from 0.001% to 20% by weight of the total weight of the
composition, such as for example from 0.01% to 10% by weight of the
total weight of the composition.
[0166] In one embodiment of the invention, namely within the
ready-to-use composition, said at least one composition (A) and
said at least one composition (B) can further comprise at least one
polymer chosen from cationic and amphoteric polymers, such as
substantive polymers.
[0167] Cationic Polymers
[0168] As used herein, "cationic polymer" refers to polymers chosen
from polymers comprising at least one cationic group and polymers
comprising at least one group which can be ionized to form cationic
groups.
[0169] Representative cationic polymers which may be used in
accordance with the present invention include any of those already
known to improve at least one cosmetic property of hair, such as,
for example, those described in patent application EP-A-0 337 354
and in French patent applications FR-A-2 270 846, 2 383 660, 2 598
611, 2 470 596 and 2 519 863, the disclosures of which are
incorporated herein by reference.
[0170] According to the present invention, the at least one
cationic polymer may be chosen from polymers comprising at least
one unit, wherein said at least one unit comprises at least one
group chosen from primary amine groups, secondary amine groups,
tertiary amine groups and quaternary amine groups, wherein said at
least one group forms part of the polymer skeleton, or is carried
by at least one lateral substituent on said polymer skeleton.
[0171] According to the present invention, the at least one
cationic polymer has a number-average molecular mass generally
ranging for example from 500 to 5.times.10.sup.6, such as from
1.times.10.sup.3 to 3.times.10.sup.6.
[0172] The at least one cationic polymer may, for example, be
chosen from polymers of quaternary polyammonium type, polymers of
polyamino amide type and polymers of polyamine type. Such types of
polymers are known in the art. They are for example described in
French patents Nos. 2,505,348 and 2,542,997, the disclosures of
which are incorporated by reference herein.
[0173] Non-limiting examples of cationic polymers include:
[0174] (1) homo- and co-polymers derived from at least one monomer
chosen from acrylic esters, methacrylic esters and amides, wherein
said homo- and co-polymers comprise at least one unit chosen from
units of formulae: 6
[0175] wherein:
[0176] R.sub.3, which may be identical or different, are each
chosen from hydrogen atoms and CH.sub.3 groups;
[0177] A, which may be identical or different, are each chosen from
linear and branched alkyl groups comprising from 1 to 6 carbon
atoms, such as 2 and 3 carbon atoms, and hydroxyalkyl groups
comprising from 1 to 4 carbon atoms;
[0178] R.sub.4, R.sub.5 and R.sub.6, which may be identical or
different, are each chosen from alkyl groups comprising from 1 to
18 carbon atoms, such as from 1 to 6 carbon atoms, and benzyl
groups;
[0179] R.sub.1 and R.sub.2, which may be identical or different,
are each chosen from hydrogen atoms and alkyl groups comprising
from 1 to 6 carbon atoms, such as methyl and ethyl;
[0180] X.sup.- is an anion chosen from anions derived from at least
one inorganic acid and anions derived from at least one organic
acid, such as methosulfate anions and halides, such as chlorides
and bromides.
[0181] Copolymers of family (1) may further comprise at least one
unit derived from at least one comonomer chosen from vinyllactams,
vinyl esters, acrylamides, methacrylamides, diacetone acrylamides,
acrylamides and methacrylamides substituted on the nitrogen with at
least one group chosen from (C.sub.1-C.sub.4) alkyls, acrylic
acids, methacrylic acids, acrylic esters, and methacrylic esters.
Non-limiting examples of vinyllactams include vinylpyrrolidone and
vinylcaprolactam.
[0182] Non-limiting examples of copolymers of family (1)
include:
[0183] copolymers derived from at least one monomer of (i)
acrylamide and (ii) dimethylaminoethyl methacrylate quaternized
with at least one group chosen from dimethyl sulfate and dimethyl
halide, such as the product sold under the name HERCOFLOC by the
company Hercules;
[0184] copolymers derived from at least one monomer of (i)
acrylamide and (ii) methacryloyloxyethyltrimethylammonium chloride
described, for example, in patent application EP-A-080 976, the
disclosure of which is incorporated herein by reference, and which
is sold under the name BINA QUAT P 100 by the company Ciba
Geigy;
[0185] copolymers derived from at least one monomer of (i)
acrylamide and (ii) methacryloyloxyethyltrimethylammonium
methosulfate, such as, for example, copolymers sold under the name
RETEN by the company Hercules;
[0186] quaternized and non-quaternized
vinylpyrrolidone/dialkylaminoalkyl acrylate copolymers and
quaternized and non-quaternized vinylpyrrolidone/dialkylaminoalkyl
methacrylate copolymers, such as the products sold under the name
"GAFQUAT" by the company ISP, such as, for example, "GAFQUAT 734"
or "GAFQUAT 755" and the products known as "COPOLYMER 845, 958 and
937". These polymers are described in detail in French patents 2
077 143 and 2 393 573, the disclosures of which are incorporated
herein by reference;
[0187] dimethylaminoethyl
methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as
the product sold under the name GAFFIX VC 713 by the company
ISP;
[0188] vinylpyrrolidone/methacrylamidopropyidimethylamine
copolymers, such as the product sold under the name STYLEZE CC 10
by ISP; and
[0189] quaternized
vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such
as the product sold under the name "GAFQUAT HS 100" by the company
ISP;
[0190] (2) cellulose ether derivatives comprising quaternary
ammonium groups, such as those described in French patent
1,492,597, the disclosure of which is incorporated herein by
reference, and polymers sold under the names "JR" (JR 400, JR 125
and JR 30M) and "LR" (LR 400, or LR 30M) by the company Union
Carbide Corporation. These polymers are also defined in the CTFA
dictionary as quaternary ammoniums of hydroxyethylcellulose which
have reacted with an epoxide substituted with a trimethylammonium
group;
[0191] (3) cationic cellulose derivatives such as cellulose
copolymers and cellulose derivatives grafted with at least one
water-soluble monomer of quaternary ammonium, such as those
described in U.S. Pat. No. 4,131,576, the disclosure of which is
incorporated herein by reference, such as hydroxyalkylcelluloses
(such as, for example, hydroxymethylcelluloses,
hydroxyethylcelluloses and hydroxypropylcelluloses, wherein said
hydroxyalkylcelluloses are grafted with at least one salt chosen
from, for example, methacryloylethyltrimethylammonium salts,
methacrylamidopropyltrimethylammonium salts and
dimethyldiallylammonium salts). For example, commercial products
corresponding to the aforementioned cationic cellulose derivatives
include the products sold under the names "CELQUAT L 200" and
"CELQUAT H 100" by the company National Starch;
[0192] (4) cationic polysaccharides, such as those described in
U.S. Pat. Nos. 3,589,578 and 4,031,307, the disclosures of which
are incorporated herein by reference, such as guar gums comprising
at least one cationic trialkylammonium group. For example, guar
gums modified with at least one salt, such as a chloride salt, of
2,3-epoxypropyltrimethylammonium may be used in the present
invention. Such products are sold in particular under the trade
names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 and JAGUAR C162 by the
company Meyhall;
[0193] (5) polymers comprising (i) at least one piperazinyl unit
and (ii) at least one group chosen from divalent alkylene groups
and divalent hydroxyalkylene groups, wherein said at least one
group optionally comprises at least one chain chosen from straight
chains and branched chains, wherein said at least one chain is
optionally interrupted by at least one entity chosen from oxygen
atoms, sulfur atoms, nitrogen atoms, aromatic rings and
heterocyclic rings, the oxidation products of said polymers and the
quaternization products of said polymers. For example, such
polymers are described in French patents 2,162,025 and 2,280,361,
the disclosures of which are incorporated herein by reference;
[0194] (6) water-soluble polyamino amides which may be prepared by
at least one polycondensation reaction of at least one acidic
compound and at least one polyamine compound, wherein said
polyamino amides may be crosslinked with at least one crosslinking
agent chosen from epihalohydrins, diepoxides, dianhydrides,
unsaturated dianhydrides, bis-unsaturated derivatives,
bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines, bis-alkyl
halides and oligomers derived from reaction of at least one
difunctional compound with at least one compound chosen from
bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines, bis-alkyl
halides, epihalohydrins, diepoxides and bis-unsaturated
derivatives, wherein said crosslinking agent may be used in a
proportion generally ranging from 0.025 mol to 0.35 mol per amine
group of said polyamino amide, wherein said polyamino amides may
optionally be alkylated, and wherein if said polyamino amides
comprise at least one tertiary amine group, said polyamino amides
may optionally be quaternized. For example, such polymers are
described in French patents 2,252,840
[0195] (7) polyamino amide derivatives derived from condensation of
at least one polyalkylene polyamine with at least one
polycarboxylic acid, followed by alkylation with at least one
bifunctional agent. Non-limiting examples of such polyamino amide
derivatives include adipic
acid/dialkylaminohydroxyalkyldialkylenetriamine polymers wherein
the alkyl group comprises from 1 to 4 carbon atoms, such as methyl
groups, ethyl groups and propyl groups. For example, such polymers
are described in French patent 1,583,363, the disclosure of which
is incorporated herein by reference.
[0196] Other non-limiting examples of such derivatives include the
adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers
sold under the name "CARTARETINE F, F4 or F8" by the company
Sandoz.
[0197] (8) polymers derived from the reaction of (i) at least one
polyalkylene polyamine comprising two primary amine groups and at
least one secondary amine group with (ii) at least one dicarboxylic
acid chosen from diglycolic acid and saturated aliphatic
dicarboxylic acids comprising from 3 to 8 carbon atoms. According
to the present invention, the molar ratio of the at least one
polyalkylene polyamine to the at least one dicarboxylic acid
generally ranges from 0.8:1 to 1.4:1. The polyamino amide resulting
from the above reaction may be reacted with epichlorohydrin in a
molar ratio of epichlorohydrin to the at least one secondary amine
group of the polyamino amide generally ranging from 0.5:1 to 1.8:1.
For example, such polymers are described in U.S. Pat. Nos.
3,227,615 and 2,961,347, the disclosures of which are incorporated
herein by reference.
[0198] Polymers of this type are sold in particular under the name
"HERCOSETT 57" by the company Hercules Inc. and under the name "PD
170" or "DELSETTE 101" by the company Hercules in the case of
adipic acid/epoxypropyl/diethylenetriamine copolymers.
[0199] (9) cyclopolymers of alkyldiallylamine and cyclopolymers of
dialkyldiallylammonium, such as homopolymers and copolymers
comprising, as a constituent of the chain, at least one unit chosen
from units of formulae (VI) and (VI'): 7
[0200] wherein:
[0201] k and t, which may be identical or different, are each
chosen from 0 and 1, with the proviso that the sum of k+t is equal
to 1;
[0202] R.sub.12, which may be identical or different, are each
chosen from hydrogen atoms and methyl groups;
[0203] R.sub.10 and R.sub.11, which may be identical or different,
are each chosen from alkyl groups comprising from 1 to 22 carbon
atoms, such as from 1 to 4 carbon atoms, hydroxyalkyl groups, such
as hydroxy alkyl groups wherein the alkyl radical comprises from 1
to 5 carbon atoms, and C.sub.1-C.sub.4 amidoalkyl groups;
[0204] R.sub.10 and R.sub.11, together with the nitrogen atom to
which they are commonly bonded, may additionally form at least one
heterocyclic group, such as piperidyl groups and morpholinyl
groups;
[0205] Y.sup.- is an anion, such as bromide, chloride, acetate,
borate, citrate, tartrate, bisulfate, bisulfite, sulfate and
phosphate. For example, such polymers are described in French
patent 2,080,759 and in its Certificate of Addition 2,190,406, the
disclosures of which are incorporated herein by reference.
[0206] Non-limiting examples of the polymers defined above include
the dimethyidiallylammonium chloride homopolymer sold under the
name "MERQUAT 100" by the company Calgon (and its homologues of low
weight-average molecular mass) and copolymers of
diallyidimethylammonium chloride and of acrylamide, sold under the
name "MERQUAT 550".
[0207] (10) quaternary diammonium polymers comprising repeating
units of formula (VII): 8
[0208] wherein:
[0209] R.sub.13, R.sub.14, R,.sub.5 and R.sub.16, which may be
identical or different, are each chosen from aliphatic groups
comprising from 1 to 20 carbon atoms, alicyclic groups comprising
from 2 to 20 carbon atoms, arylaliphatic groups comprising from 5
to 20 carbon atoms, and lower hydroxyalkyl groups; and
[0210] additionally at least two of said R.sub.13, R.sub.14,
R.sub.15 and R.sub.16, together with the nitrogen atoms to which
they are attached, may form at least one heterocycle optionally
comprising an additional heteroatom other than nitrogen; and
[0211] additionally, R.sub.13, R.sub.14, R.sub.15 and R.sub.16,
which may be identical or different, may each be chosen from linear
and branched C.sub.1-C.sub.6 alkyl groups substituted with at least
one group chosen from nitrile groups, ester groups, acyl groups,
amide groups and groups chosen from groups of formulae
--CO--O--R.sub.17--D and --CO--NH--R.sub.17--D wherein R.sub.17 is
chosen from alkylene groups and D is chosen from quaternary
ammonium groups;
[0212] A.sub.1 and B.sub.1, which may be identical or different,
are each chosen from polymethylene groups comprising from 2 to 20
carbon atoms, chosen from linear and branched, saturated and
unsaturated polymethylene groups wherein said polymethylene groups
may optionally comprise, optionally linked to and optionally
intercalated in the main chain, at least one entity chosen from
aromatic rings, oxygen atoms, sulfur atoms, sulfoxide groups,
sulfone groups, disulfide groups, amino groups, alkylamino groups,
hydroxyl groups, quaternary ammonium groups, ureido groups, amide
groups and ester groups; and
[0213] X.sup.-- is an anion chosen from anions derived from
inorganic acids and anions derived from organic acids; and
[0214] A.sub.1, R.sub.13 and R.sub.15 may optionally form, together
with the nitrogen atoms to which they are attached, at least one
piperazine ring;
[0215] with the proviso that if A.sub.1 is chosen from linear and
branched, saturated and unsaturated alkylene groups and linear and
branched, saturated and unsaturated hydroxyalkylene groups, B.sub.1
may also be chosen from groups of formula:
--(CH.sub.2).sub.n--CO--D--OC--(CH.sub.2).sub.n--
[0216] wherein:
[0217] n is a number such that the overall quaternary diammonium
polymer has a number-average molecular mass generally ranging for
example from 1000 to 100,000;
[0218] --D is chosen from:
[0219] a) glycol residues of formula: --O--Z--O--, wherein Z is
chosen from linear and branched hydrocarbon groups and groups
chosen from groups of formulae:
--(CH.sub.2--CH.sub.2--O).sub.x--CH.sub.2--CH.sub.2--; and
--[CH.sub.2--CH(CH.sub.3)--O].sub.y--CH.sub.2--CH(CH.sub.3)--
[0220] wherein x and y, which may be identical or different, are
each chosen from integers ranging from 1 to 4 (in which case x and
y represent a defined and unique degree of polymerization) and any
number ranging from 1 to 4 (in which case x and y represent an
average degree of polymerization);
[0221] b) bis-secondary diamine residues such as piperazine
derivatives;
[0222] c) bis-primary diamine residues chosen from residues of
formula: --NH--Y--NH--, wherein Y is chosen from linear and
branched hydrocarbon groups and residues of formula
--CH.sub.2--CH.sub.2--S--S--CH.sub.2--CH.s- ub.2--; and
[0223] d) ureylene groups of formula: --NH--CO--NH--.
[0224] In one embodiment, X.sup.-- is an anion chosen from chloride
ions and bromide ions. According to the present invention, the
quarternary diammonium polymers have a number-average molecular
mass generally ranging from 1000 to 100,000.
[0225] For example, polymers of this type are described in French
Patent Nos. 2,320,330, 2,270,846, 2,316,271, 2,336,434 and
2,413,907 and U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614,
2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432,
3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653,
4,026,945 and 4,027,020, the disclosures of which are incorporated
herein by reference.
[0226] Further, according to the present invention, polymers
comprising repeating units of formula (a) may be used: 9
[0227] wherein:
[0228] R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be
identical or different, are each chosen from alkyl groups
comprising from 1 to 4 carbon atoms and hydroxyalkyl groups
comprising from 1 to 4 carbon atoms;
[0229] n and p, which may be identical or different, are each
chosen from integers ranging from 2 to 20; and
[0230] X.sup.- is an anion chosen from anions derived from
inorganic acids and anions derived from organic acids.
[0231] (11) polyquaternary ammonium polymers comprising repeating
units of formula (VIII): 10
[0232] wherein:
[0233] p is an integer ranging from 1 to 6,
[0234] D is chosen from direct bonds and --(CH.sub.2).sub.r--CO--
groups, wherein r is a number equal to 4 or 7, and
[0235] X.sup.- is an anion chosen from anions derived from
inorganic acids and anions derived from organic acids.
[0236] For example, such compounds are described in patent
application EP-A-122,324, the disclosure of which is incorporated
by reference herein, and may be prepared according to the
procedures described in the U.S. Pat. Nos. 4,157,388, 4,390,689,
4,702,906, and 4,719,282, the disclosures of which are incorporated
by reference herein.
[0237] Among these, there may be mentioned for example the products
"Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175" sold
by the company Miranol.
[0238] (12) quaternary polymers of vinylpyrrolidone and quaternary
polymers of vinylimidazole, such as, for example, the products sold
under the names LUVIQUAT FC 905, FC 550 and FC 370 by the company
BASF.
[0239] (13) polyamines, such as POLYQUART H sold by Henkel under
the reference name "POLYETHYLENE GLYCOL (15) TALLOW POLYAMINE" in
the CTFA dictionary.
[0240] (14) crosslinked
(meth)acryloyloxy(C.sub.1-C.sub.4)alkyltri(C.sub.1-
-C.sub.4)alkylammonium salt polymers, such as the polymers derived
from homopolymerization of dimethylaminoethyl methacrylate
quaternized with methyl chloride and polymers derived from
copolymerization, for example, of acrylamide with
dimethylaminoethyl methacrylate quaternized with a methyl halide
(such as methyl chloride), wherein the homo- or copolymerization is
followed by crosslinking with at least one compound comprising
olefinic unsaturation, such as methylenebisacrylamide. For example,
a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium
chloride copolymer (20/80 by weight) in the form of a dispersion
comprising about 50% by weight of said copolymer in mineral oil may
be used. This dispersion is sold under the name "SALCARE SC 92" by
the company Allied Colloids. Further, a crosslinked
methacryloyloxyethyltrime- thylammonium chloride homopolymer
comprising about 50% by weight of the homopolymer in mineral oil or
in a liquid ester may be used. These dispersions are sold under the
names "SALCARE SC 95" and "SALCARE SC 96" by the company Allied
Colloids.
[0241] Other cationic polymers which may be used as the at least
one cationic polymer according to the present invention are
polyalkyleneimines (such as polyethyleneimines), polymers
comprising at least one vinylpyridine unit, polymers comprising at
least one vinylpyridinium unit, condensates of polyamines,
condensates of epichlorohydrin, quaternary polyureylenes and chitin
derivatives.
[0242] Other embodiments of the invention use cationic polymers
chosen from the polymers of (1), (9), (10), (11) and (14).
Specifically, polymers of formulae (W) and (U) can be used: 11
[0243] such as those of which the molecular weight, determined by
gel chromatography, ranges from 9500 to 9900; 12
[0244] and in particular those of which the molecular weight,
determined by gel chromatography, is approximately 1200.
[0245] Generally, the cationic polymers are present in an amount
ranging for example from 0.01% to 10% by weight relative to the
total weight of the final composition, such as from 0.05% to 5% by
weight relative to the total weight of the final composition, and
further such as from 0.1% to 3% by weight relative to the total
weight of the final composition.
[0246] Amphoteric Polymers
[0247] The amphoteric polymers which can be used in the present
invention can be chosen from polymers comprising K and M units
distributed statistically in the polymer chain, wherein:
[0248] K is a unit derived from a monomer comprising at least one
basic nitrogen atom and M is a unit derived from an acid monomer
comprising at least one group chosen from carboxylic groups and
sulfonic groups; or alternatively
[0249] K and M, which are identical or different, are each groups
chosen from groups derived from zwitterionic monomers of
carboxybetaines and groups derived from zwitterionic monomers of
sulfobetaines; or alternatively
[0250] K and M, which are identical or different, are each chosen
from polymers comprising cationic polymer chains comprising at
least one amine group chosen from primary, secondary, tertiary and
quaternary amine groups, wherein at least one of the amine groups
is substituted with a group chosen from carboxylic groups and
sulphonic groups linked via a hydrocarbon radical; or
alternatively
[0251] K and M form part of a chain of a polymer with an
.alpha.,.beta.-dicarboxylic ethylene unit wherein one of the
carboxylic groups has been caused to react with a polyamine
comprising at least one amine group chosen from primary amine
groups and secondary amine groups.
[0252] Representative of the film forming amphoteric polymers
defined above that can be used include the following polymers:
[0253] (1) The polymers resulting from the copolymerization of a
monomer derived from a vinyl compound substituted with a carboxylic
group such as acrylic acid, methacrylic acid, maleic acid, and
.alpha.-chloroacrylic acid, and of a basic monomer derived from a
substituted vinyl compound comprising at least one basic atom such
as dialkylaminoalkyl methacrylate and acrylate,
dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are
described in U.S. Pat. No. 3,836,537, the disclosure of which is
incorporated by reference herein. Copolymer of the sodium
acrylate/acrylamidopropyl-trimethylammonium chloride sold under the
name of "POLYQUART KE 3033" by the company HENKEL can also be
cited.
[0254] The vinyl compound can also be a salt of
dialkyidiallylammonium such as diethyldiallylammonium chloride. The
copolymers of acrylic acid and the latter monomer are proposed
under the name "MERQUAT 280", "MERQUAT 295" and "MERQUAT PLUS 3330"
by the company CALGON.
[0255] (2) The polymers comprising units derived from:
[0256] a) at least one monomer chosen from acrylamides substituted
on the nitrogen by an alkyl radical and methacrylamides substituted
on the nitrogen by an alkyl radical,
[0257] b) at least one acidic comonomer comprising at least one
reactive carboxylic group, and
[0258] c) at least one basic comonomer such as comonomers chosen
from esters of acrylic acid and esters of methacrylic acid, said
esters being substituted with at least one amine chosen from
primary, secondary, tertiary and quaternary amines, and the product
of quaternization of dimethylaminoethyl methacrylate with a sulfate
chosen from dimethyl sulfate and diethyl sulfate.
[0259] Some embodiments according to the invention utilize
N-substituted acrylamides and methacrylamides comprising
(C.sub.2-C.sub.12)alkyl groups, such as N-ethylacrylamide,
N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide,
N-decylacrylamide, and N-dodecylacrylamide, as well as the
corresponding methacrylamides.
[0260] The acidic comonomers can be chosen, for example, from
acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids
as well as the (C.sub.1-C.sub.4)alkyl monoesters of entities chosen
from maleic anhydride, fumaric anhydride, maleic acid, and fumaric
acid.
[0261] The basic comonomers can be chosen, for example, from
methacrylates of aminoethyl, butylaminoethyl,
N,N'-dimethylaminoethyl, and N-tert-butylaminoethyl.
[0262] Additionally, the copolymers having the CTFA name (4th
edition, 1991)
Octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer
such as the products sold under the name AMPHOMER and LOVOCRYL 47
by the company NATIONAL STARCH can also be used.
[0263] (3) The partially and completely alkylated and crosslinked
polyaminoamides derived from polyaminoamides of formula:
CO--R.sub.27--CO--Z (VIII)
[0264] wherein:
[0265] R.sub.27 is a divalent group chosen from groups derived from
saturated dicarboxylic acids, groups derived from dicarboxylic
aromatic acids, groups derived from mono- and dicarbocylic
aliphatic acids comprising at least one ethylenic double bond,
groups derived from an ester of (C.sub.1-C.sub.6)alkanols of said
acids, and groups derived from the addition of any one of said
aforementioned acids with an amine chosen from bis-primary and
bis-secondary amines, and
[0266] Z is a divalent group derived from polyalkylene-polyamines
chosen from bis-primary, mono- and bis-secondary
polyalkylene-polyamines, for example, Z represents:
[0267] a) in an amount ranging from 60 mol % to 100 mol %, the
group
--N.sub.H--(CH.sub.2).sub.x--N.sub.H (IX)
[0268] wherein x=2 and p=2 or 3, or alternatively x=3 and p=2,
[0269] it being understood that group Z of formula a) is derived
from a compound chosen from diethylenetriamine,
triethylenetetraamine and dipropylenetriamine;
[0270] b) in an amount ranging from 0 mol % to 40 mol %, (1) said
groups (IX) above in which x=2 and p=1 and which said group is
derived from a compound chosen from ethylenediamine, and (2) groups
derived from piperazine: 13
[0271] c) in an amount ranging from 0 mol % to 20 mol %, the
polyalkylene-polyamine group --NH--(CH.sub.2).sub.6--NH--, which is
derived from hexamethylenediamine, wherein said
polyalkylene-polyamine group is crosslinked by adding a
bifunctional crosslinking agent (chosen from the epihalohydrins,
diepoxides, dianhydrides, and bis-unsaturated derivatives) present
in an amount ranging from 0.025 mol to 0.35 mol of crosslinking
agent per amine group of the polyamino amide and alkylated by the
action of at least one compound chosen from acrylic acid,
chloroacetic acid, alkanesultones, and salts thereof.
[0272] The saturated dicarboxylic acids are for example chosen from
saturated (C.sub.6-C.sub.10) dicarboxylic acids such as adipic,
2,2,4-trimethyladipic and 2,4,4-trimethyladipic acid.
[0273] Representative dicarboxylic aromatic acids include for
example (C.sub.6-C.sub.10) dicarboxylic aromatic acids, such as
terephthalic acid. And representative mono- and dicarboxylic
aliphatic acids comprising at least one ethylenic double bond
include for example acrylic, methacrylic and itaconic acids.
[0274] The alkanesultones used in the alkylation can, for example,
be chosen from propanesultone and butanesultone, and the salts of
the alkylating agents can be chosen from sodium and potassium salts
of said alkylating agents.
[0275] (4) The polymers comprising zwitterionic units of formula:
14
[0276] wherein:
[0277] R.sub.28 is chosen from polymerizable unsaturated groups
such as acrylate, methacrylate, acrylamide and methacrylamide
groups,
[0278] y and z, which can be identical or different, are each
chosen from integers ranging from 1 to3,
[0279] R.sub.29 and R.sub.30, which may be identical or different,
are each chosen from hydrogen, and methyl, ethyl and propyl
groups,
[0280] R.sub.31 and R.sub.32, which may be identical or different,
are each chosen from hydrogen and alkyl groups, provided that the
sum of the carbon atoms in R.sub.3, and R.sub.32 does not exceed
10.
[0281] The polymers comprising such units may also comprise units
derived from nonzwitterionic monomers such as dimethylaminoethyl
acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl
acrylate, diethylaminoethyl methacrylate, alkyl acrylates, alkyl
methacrylates, alkyl acrylamides, alkyl methacrylamides, and vinyl
acetate.
[0282] By way of example, there may be mentioned the copolymer of
methyl methacrylate/methyl dimethylcarboxymethylammonioethyl
methacrylate such as the product sold under the name DIAFORMER Z301
by the company SANDOZ.
[0283] (5) The polymers derived from chitosan comprising at least
one monomeric unit chosen from formulae (D), (E) and (F), which are
described for example in U.S. Pat. No. 4,996,059, the disclosure of
which is herein incorporated by reference: 15
[0284] wherein said unit (D) is present in an amount ranging for
example from 0% to 30%, by weight relative to the total weight of
said polymer, said unit (E) is present in an amount ranging for
example from 5% to 50% by weight relative to the total weight of
said polymer, and said unit (F) is present in an amount ranging for
example from 30% to 90% by weight relative to the total weight of
said polymer,
[0285] and wherein in said unit (F), R.sub.33 is chosen from groups
of formula: 16
[0286] wherein:
[0287] q is equal to 0 or 1, and (i) when q is equal to 0,
R.sub.34, R.sub.35 and R.sub.36, which may be identical or
different, are each chosen from:
[0288] hydrogen,
[0289] methyl, hydroxyl, acetoxy, and amino groups,
[0290] monoalkylamine and dialkylamine groups optionally
interrupted by at least one nitrogen atom and/or optionally
substituted with at least one group chosen from amine, hydroxyl,
carboxyl, alkylthio and sulfonic groups, and
[0291] alkylthio groups wherein said alkyl portion of said
alkylthio group carries an amino group,
[0292] provided that at least one of said R.sub.34, R.sub.35 and
R.sub.36 groups is chosen from hydrogen; and
[0293] (ii) when q is equal to 1, R.sub.34, R.sub.35 and R.sub.36,
which may be identical or different, are each chosen from
hydrogen,
[0294] and the salts formed by these polymers (5) with bases, and
the salts formed by these polymers (5) with acids.
[0295] (6) The polymers derived from the N-carboxyalkylation of
chitosan such as N-carboxymethyl chitosan and N-carboxybutyl
chitosan sold under the name "EVALSAN" by the company JAN
DEKKER.
[0296] (7) The polymers of formula (XI), which are described for
example in French Patent 1400366, the disclosure of which is
incorporated by reference herein: 17
[0297] wherein:
[0298] r is chosen such that the number-average molecular weight of
said polymer ranges from 500 to 6,000,000, such as from 1000 to
1,000,000.
[0299] R.sub.37 is chosen from hydrogen and CH.sub.3O,
CH.sub.3CH.sub.2O, and phenyl groups,
[0300] R.sub.38 and R.sub.39, which are identical or different, are
each chosen from hydrogen and lower alkyl groups such as methyl and
ethyl,
[0301] R.sub.40 is chosen from lower alkyl groups such as methyl
and ethyl and groups of formula: --R.sub.41--N(R.sub.39).sub.2,
comprising up to 6 carbon atoms, wherein R.sub.39 is as defined
above and R.sub.41 is defined below,
[0302] R.sub.41 is chosen from --CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--CH.sub.2--, and
--CH.sub.2--CH(CH.sub.3)--.
[0303] (8) Amphoteric polymers of the --D--X--D--X-- type, which
are described for example in U.S. Pat. No. 4,996,059, the
disclosure of which is herein incorporated by reference, chosen
from:
[0304] a) polymers derived from reaction of chloroacetic acid or
sodium chloroacetate with at least one compound comprising at least
one unit of formula (XII):
--D--X--D--X--D-- (XII)
[0305] wherein D is a group: 18
[0306] and X is chosen from the symbols E and E', wherein E and E',
which are identical or different, are each chosen from bivalent
groups chosen from alkylene groups comprising at least one chain
chosen from linear and branched chains comprising up to 7 carbon
atoms in the principal chain, wherein said principal chain is
optionally substituted with at least one hydroxyl group, and
wherein said alkylene groups optionally comprise at least one atom
chosen from oxygen atoms, nitrogen atoms and sulfur atoms, wherein
said at least one optional atom is present in the form of at least
one group chosen from ether, thioether, sulfoxide, sulfone,
sulfonium, alkylamine and alkenylamine groups, and hydroxyl,
benzylamine, amine oxide, quaternary ammonium, amide, imide,
alcohol, ester and urethane groups, and wherein said alkylene
groups optionally comprise from 1 to 3 rings chosen from aromatic
rings and heterocyclic rings,
[0307] b) polymers of formula:
--D--X--D--X-- (XIII)
[0308] wherein:
[0309] D is a group: 19
[0310] X is chosen from the symbols E and E' and wherein at least
one X is chosen from E',
[0311] E is chosen from bivalent groups chosen from alkylene groups
comprising at least one chain chosen from linear and branched
chains comprising up to 7 carbon atoms in the principal chain,
wherein said alkylene groups are optionally substituted with at
least one hydroxyl group, and wherein said alkylene groups
optionally comprise at least one atom chosen from oxygen atoms,
nitrogen atoms, and sulfur atoms, wherein said at least one
optional atom is present in the form of at least one group chosen
from ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine
and alkenylamine groups, and hydroxyl, benzylamine, amine oxide,
quaternary ammonium, amide, imide, alcohol, ester and urethane
groups, and wherein said alkylene groups optionally comprises 1 to
3 rings chosen from aromatic rings and heterocyclic rings, and
[0312] E' is a bivalent group chosen from alkylene groups
comprising at least one chain chosen from linear and branched
chains comprising up to 7 carbon atoms in the principal chain,
wherein said principal chain is optionally substituted with at
least one hydroxyl group, and wherein said alkylene groups comprise
at least one nitrogen atom substituted with an alkyl chain, wherein
said alkyl chain is optionally interrupted by an oxygen atom and,
wherein said alkyl chain comprises at least one functional group
chosen from carboxyl and hydroxyl functional groups, and wherein
said at least one alkyl chain is betainized by reaction with a
reactant chosen from chloroacetic acid and sodium
chloroacetate.
[0313] (9) The copolymers (C.sub.1-C.sub.5)alkyl vinyl ether/maleic
anhydride partially modified by semiamidation with an
N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine or
by semiesterification with an N,N-dialkanolamine. These copolymers
may also comprise other vinyl comonomers such as
vinylcaprolactam.
[0314] The amphoteric polymers of family (1) are utilized in
certain embodiments of the invention.
[0315] According to the invention, the at least one polymer chosen
from cationic and amphoteric polymers may be present in an amount
ranging for example from 0.01% to 10% by weight relative to the
total weight of the composition, such as from 0.05% to 5% by weight
relative to the total weight of the composition, and further such
as from 0.1% to 3% by weight relative to the total weight of the
composition.
[0316] Surfactants
[0317] The ready-to-use composition according to the invention can
comprise at least one surfactant, which is present in at least one
of said at least one dyeing composition (A), said at least one
oxidizing composition (B), and said at least one dyeing composition
(A) and said at least one oxidizing composition (B).
[0318] The at least one surfactant may be chosen from anionic,
amphoteric, nonionic, zwitterionic and cationic surfactants.
[0319] Representative choices for the at least one surfactant
include the following:
[0320] (i) Anionic Surfactant(s)
[0321] Representative anionic surfactants include salts (for
example alkaline salts, such as sodium salts, ammonium salts, amine
salts, amino alcohol salts and magnesium salts) of the following
compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether
sulfates, alkylarylpolyether sulfates, monoglyceride sulfates;
alkyl sulfonates, alkyl phosphates, alkylamide sulfonates,
alkylaryl sulfonates, .alpha.-olefin sulfonates, paraffin
sulfonates; alkyl(C.sub.6-C.sub.24) sulfosuccinates,
alkyl(C.sub.6-C.sub.24) ether sulfosuccinates,
alkyl(C.sub.6-C.sub.24)amide sulfosuccinates,
alkylsulfosuccinamates alkyl(C.sub.6-C.sub.24) sulfoacetates,
acyl(C.sub.6-C.sub.24) sarcosinates, acyl(C.sub.6-C.sub.24)
glutamates, acyl isethionates, N-acyltaurates, and
alkyl(C.sub.6-C.sub.24)polyglycoside carboxylic esters such as
alkylglucoside citrates, alkylpolyglycoside tartrate,
alkylpolyglycoside sulfosuccinates, and alkyl sulfosuccinamates.
The alkyl and acyl radicals of all of these various compounds can
for example comprise from 12 to 20 carbon atoms, and the aryl
radicals can for example be chosen from phenyl and benzyl
groups.
[0322] For example, anionic surfactants can be chosen from fatty
acid salts such as the salts of oleic acid, ricinoleic acid,
palmitic acid, stearic acid, the acids of copra oil and the acids
of hydrogenated copra oil, and acyl lactylates in which the acyl
radical comprises from 8 to 20 carbon atoms. At least one weakly
anionic surfactant can also be used, such as
alkyl-D-galactosideuronic acids and their salts, as well as
polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkyl ether acids,
polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkylaryl ether
acids, polyoxyalkylenated carboxylic (C.sub.6-C.sub.24)alkyl
amidoether acids and their salts, for example, those comprising
from 2 to 50 ethylene oxide groups.
[0323] (ii) Nonionic Surfactant(s)
[0324] Useful nonionic surfactants include compounds that are well
known per se (see for example in this respect "Handbook of
Surfactants" by M. R. Porter, published by Blackie & Son
(Glasgow and London), 1991, pp. 116-178), the disclosure of which
is incorporated by reference herein. Thus, nonionic surfactants can
include alcohols, .alpha.-diols, and polyethoxylated alkylphenols
and polypropoxylated alkylphenols comprising at least one fatty
chain comprising for example from 8 to 18 carbon atoms, wherein the
number of ethylene oxide and propylene oxide groups can range for
example from 2 to 50. Additionally, copolymers of ethylene oxide,
copolymers of propylene oxide, condensates of ethylene oxide with
fatty alcohols, condensates of propylene oxide with fatty alcohols,
polyethoxylated fatty amides, such as those comprising from 2 to 30
mol of ethylene oxide, polyglycerolated fatty amides on average
comprising 1 to 5 glycerol groups, such as from 1.5 to 4,
polyethoxylated fatty amines comprising for example from 2 to 30
mol of ethylene oxide, oxyethylenated fatty acid esters of sorbitan
comprising from 2 to 30 mol of ethylene oxide, fatty acid esters of
sucrose, fatty acid esters of polyethylene glycol,
alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides,
such as the oxides of (C.sub.10-C.sub.14) alkylamines, and
N-acylaminopropylmorpholine oxides can also be used. It will be
noted that the alkylpolyglycosides are nonionic surfactants that
can be suitable in the context of the present invention.
[0325] (iii) Amphoteric or Zwitterionic Surfactant(s)
[0326] Representative amphoteric and zwitterionic surfactants can
be chosen from aliphatic secondary and tertiary amine derivatives
in which the aliphatic radical is chosen from linear and branched
chain radicals comprising 8 to 18 carbon atoms and comprising at
least one water-soluble anionic group (chosen for example from
carboxylate, sulfonate, sulfate, phosphate and phosphonate);
mention may also be made of (C.sub.8-C.sub.20)alkylbetaines,
sulfobetaines, (C.sub.8-C.sub.20)alkylam-
ido(C.sub.1-C.sub.6)alkylbetaines and
(C.sub.8-C.sub.20)alkylamido(C.sub.1-
-C.sub.6)alkylsulfobetaines.
[0327] Representative amine derivatives include the products sold
under the name MIRANOL, as described in U.S. Pat. Nos. 2,528,378
and 2,781,354, the disclosures of which are incorporated by
reference herein, and classified in the CTFA dictionary, 3rd
edition, 1982, under the names Amphocarboxyglycinates and
Amphocarboxypropionates, having the respective structures:
R.sub.2--CONHCH.sub.2CH.sub.2--N.sup.+(R.sub.3)(R.sub.4)(CH.sub.2COO--)
(2)
[0328] in which:
[0329] R.sub.2 is chosen from alkyl groups derived from an acid
R.sub.2--COOH present in hydrolysed copra oil, and heptyl, nonyl
and undecyl radicals,
[0330] R.sub.3 is a beta-hydroxyethyl group, and
[0331] R.sub.4 is a carboxymethyl group; and
R.sub.5--CONHCH.sub.2CH.sub.2--N(B)(C) (3)
[0332] in which:
[0333] (B) is --CH.sub.2CH.sub.2OX', wherein X' is an entity chosen
from a --CH.sub.2CH.sub.2--COOH group and a hydrogen atom,
[0334] (C) is --(CH.sub.2).sub.z-Y', wherein z=1 or 2, and wherein
Y' is an entity chosen from --COOH and --CH.sub.2--CHOH--SO.sub.3H
groups,
[0335] R.sub.5 is chosen from alkyl groups, such as (a) alkyl
groups of an acid R.sub.5--COOH present in oils chosen from copra
oil and hydrolysed linseed oil, (b) alkyl groups, such as C.sub.7,
C.sub.9, C.sub.11 and C.sub.13 alkyl groups, and (c) C.sub.17 alkyl
groups and the iso forms, and unsaturated C.sub.17 groups.
[0336] Such representative compounds are classified in the CTFA
dictionary, 5th edition, 1993, under the names disodium
cocoamphodiacetate, disodium lauroamphodiacetate, disodium
caprylamphodiacetate, disodium capryloamphodiacetate, disodium
cocoamphodipropionate, disodium lauroamphodipropionate, disodium
caprylamphodipropionate, disodium capryloamphodipropionate,
lauroamphodipropionic acid, and cocoamphodipropionic acid. By way
of example, mention may be made of the cocoamphodiacetate sold
under the trade name MIRANOL C2M Concentrate by the company RHODIA
CHIMIE.
[0337] (iv) Cationic Surfactants
[0338] Representative cationic surfactants include salts of
optionally polyoxyalkylenated primary, secondary and tertiary fatty
amines; quaternary ammonium salts such as tetraalkylammonium,
alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, and
trialkylhydroxyalkylammonium, alkylpyridinium chlorides,
alkylpyridinium bromides, imidazoline derivatives; and amine oxides
of cationic nature.
[0339] The at least one surfactant may be present in the
composition according to the invention generally in an amount
ranging for example from 0.01% to 40% by weight relative to the
total weight of the composition, such as from 0.1% to 30% by weight
relative to the total weight of the composition.
[0340] The ready-to-use composition according to the present
invention may eventually comprise, in composition (A), composition
(B), or both compositions (A) and (B), at least one other agent for
adjustment of rheology, such as agents chosen from cellulose
thickeners (for example, hydroxyethylcellulose,
hydroxypropylcellulose, and carboxymethylcellulose), guar gum and
its derivatives (for example, hydroxypropylguar), gums of microbial
origin (for example, xanthan gum and scleroglucan gum), and
synthetic thickeners not having a fatty chain (for example,
crosslinked homopolymers of acrylic acid and crosslinked
homopolymers of acrylamidopropanesulfonic acid).
[0341] Generally, these thickeners may be present in an amount
ranging for example from 0.01% to 10% by weight relative to the
total weight of the composition.
[0342] The medium of the composition appropriate for dyeing can be
an aqueous medium, optionally comprising at least one cosmetically
acceptable organic solvent.
[0343] Representative organic solvents may be chosen from alcohols,
such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and
phenylethyl alcohol. The organic solvents may also be chosen from
glycols (for example, ethyleneglycol, propyleneglycol,
butyleneglycol, dipropyleneglycol, and diethyleneglycol) and ethers
of glycols (for example, monomethyl, monoethyl and monobutyl ethers
of ethyleneglycol and for example monomethyl ether of
propyleneglycol and alkyl ethers of diethyleneglycol glycol, such
as, for example, monoethylether and monobutylether of
diethyleneglycol).
[0344] The organic solvents are generally present in an amount
ranging for example from 0.5% to 20% by weight relative to the
total weight of the composition, such as from 2% to 10% by weight
relative to the total weight of the composition.
[0345] The composition according to the invention may further
comprise an effective quantity of other agents. For example, agents
that are already known for oxidation coloration, such as various
ordinary adjuvants including sequesterizers such as EDTA and
etidronic acid, UV-screening agents, waxes, volatile and
nonvolatile, cyclic and non-cyclic, linear and branched,
organomodified (such as by amine groups) silicones, preservatives,
ceramides, pseudoceramides, vegetable, mineral and synthetic oils,
vitamins and provitamins such as panthenol, and opacifiers, may be
included.
[0346] The composition can also comprise at least one agent chosen
from reducing agents and antioxidants. Representative additional
agents may include sodium sulfite, thioglycolic acid, thiolactic
acid, sodium bisulfite, dehydroascorbic acid, hydroquinone,
2-methylhydroquinone, tert-butylhydroquinone and homogentisic acid.
Generally, such agents may be present in the an amount ranging for
example from 0.05% to 3% by weight relative to the total weight of
the composition, such as from 0.05% to 1.5% by weight relative to
the total weight of the composition.
[0347] The composition according to the invention may also comprise
at least one fatty alcohol. The at least one fatty alcohol
includes, but is not limited to, fatty alcohols chosen from fatty
alcohols, and mixtures of fatty alcohols. The expression fatty
alcohols includes, but is not limited to, linear and branched,
saturated and unsaturated fatty alcohols. Representative fatty
alcohols may be used include lauryl, cetyl, stearyl and oleyl
alcohols. The at least one fatty alcohol may be present in an
amount ranging for example from 0.001% to 20% by weight relative to
the total weight of the composition.
[0348] One skilled in the art should take care to select said
optionally complementary compounds, such that the advantageous
properties intrinsically associated with the dye composition
according to the invention are not, or are not substantially,
adversely affected by the additions envisaged.
[0349] In the ready-to-use composition, said at least one
composition (B) may comprise at least one oxidizing agent chosen,
for example, from hydrogen peroxide, urea peroxide, alkali metal
bromates and ferricyanides, and persalts such as perborates and
persulfates. More specifically, hydrogen peroxide may be used. This
oxidizing agent is advantageously constituted by an oxygenated
aqueous solution of which the titre may range from 1 to 40 in
volume, such as from 5 to 40.
[0350] As an oxidizing agent, at least one oxidation-reduction
enzyme such as laccases, peroxydases and 2-electron oxydoreductases
(such as uricase), if necessary in the presence of their respective
donor or cofactor, may also be used.
[0351] The pH of the dyeing composition (A) or of the ready-to-use
composition applied to the keratin fibers [composition resulting
from combining the dye composition (A) and the oxidizing
composition (B)], generally ranges from 4 to 12, such as from 6 to
11, and may be adjusted to the desired value by means of at least
one agent chosen from acidifying and basifying agents well-known in
the art of dyeing keratin fibers.
[0352] Representative basifying agents include aqueous ammonia,
alkali metal carbonates, alkanolamines such as mono-, di- and
triethanolamines and derivatives thereof, hydroxyalkylamines and
oxyethylenated and oxypropylenated ethylenediamines, sodium and
potassium hydroxide and compounds of formula (XIV): 20
[0353] wherein:
[0354] R is a propylene residue optionally substituted with a group
chosen from hydroxyl and C.sub.1-C.sub.4 alkyl groups;
[0355] R.sub.42, R.sub.43, R.sub.44 and R.sub.45, which may be
identical or different, are each chosen from hydrogen,
C.sub.1-C.sub.4 alkyl groups and C.sub.1-C.sub.4 hydroxyalkyl
groups.
[0356] Representative acidifying agents include, classically, by
way of example, organic and inorganic acids such as hydrochloric
acid, orthophosphoric acid, and carboxylic acids such as tartaric
acid, citric acid, lactic acid and sulfonic acids.
[0357] One dyeing method according to the invention comprises
applying on dry or wet keratin fibers, such as human keratin fibers
like hair, at least one ready-to-use cosmetic composition, prepared
at the time of use from at least one composition (A) and at least
one composition (B), leaving said at least one ready-to-use
composition on said keratin fibers for a time ranging from 1 to 60
minutes, such as from 10 to 45 minutes, rinsing said keratin
fibers, optionally shampooing said keratin fibers, rinsing said
keratin fibers after said optional shampooing, and drying said
keratin fibers, wherein said at least one ready-to-use cosmetic
composition comprises:
[0358] at least one composition (A) comprising, in a dyeing
medium:
[0359] (1) at least one oxidation dye,
[0360] (2) at least one thickening polymer comprising at least one
fatty chain, and
[0361] (3) at least one fatty alcohol chosen from monoglycerolated
and polyglycerolated fatty alcohols, and
[0362] at least one composition (B) comprising at least one
oxidizing agent.
[0363] Another process comprises applying on dry or wet keratin
fibers, such as human keratin fibers like hair, at least one
ready-to-use cosmetic composition, prepared at the time of use from
at least one composition (A'), at least one composition (A"), and
at least one composition (B), leaving said at least one
ready-to-use composition on said keratin fibers for a resting time
ranging from 1 to 60 minutes, such as from 10 to 45 minutes,
rinsing said keratin fibers, optionally shampooing said keratin
fibers, and after said optional shampooing again rinsing and drying
said keratin fibers, wherein said composition comprises:
[0364] at least one composition (A') comprising at least one
oxidation dye and at least one fatty alcohol chosen from
monoglycerolated and polyglycerolated fatty alcohols,
[0365] at least one composition (A") comprising at least one
thickening polymer comprising at least one fatty chain,
[0366] at least one composition (B) comprising at least one
oxidizing agent, and
[0367] wherein said composition comprising said at least one
compositions (A'), (A") and (B) is prepared by combining said at
least one compositions (A'), (A"), and (B) at the moment of
use.
[0368] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties such as molecular weight,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should at least be construed in
light of the number of reported significant digits and by applying
ordinary rounding techniques. Notwithstanding that the numerical
ranges and parameters setting forth the broad scope of the
invention are approximations, the numerical values set forth in the
specific examples are reported as precisely as possible. Any
numerical value, however, inherently contain certain errors
necessarily resulting from the standard deviation found in their
respective testing measurements.
[0369] Concrete examples illustrating the invention are indicated
below without however exhibiting a limiting character.
EXAMPLES
[0370] The following compositions were prepared:
1 Oxidizing composition: Fatty alcohol 2.3 g Oxyethylenated fatty
alcohol 0.6 g Fatty amide 0.9 g Glycerin 0.5 g Hydrogen peroxide
7.5 g Perfume qs Demineralized water qs 100 g
[0371]
2 Dyeing composition: (expressed in grams) Mixture of C18 to C24
linear alcohols [C18/C20/C22/C24, 3 7/58/30/6] (NAFOL 20-22) . . .
Mixture of polyglycerolated C18 to C24 linear alcohols 1.35
[C18/C20/C22/C24, 7/58/30/6] containing 6 mol of glycerol . . .
Polyglycerolated cetearyl alcohol containing 2 mol of 4 glycerol .
. . Polyglycerolated cetearyl alcohol containing 6 mol of 2
glycerol . . . Oleic acid . . . 2.6 Glycol distearate . . . 2
Propylene glycol . . . 5 Monoisopropanolamide of copra acids . . .
2 Aculyn 44 sold by the company ROHM & HAAS . . . 1.4 AS*
Crosslinked polyacrylic acid . . . 0.6 Cationic polymer of formula
(W) . . . 3 AS* Merquat 100 sold by the company CALGON . . . 0.4
AS* Reducing agents . . . 0.7 Seqestrants . . . 0.2
1,3-Dihydroxybenzene (resorcinol) . . . 0.6 1,4-Diaminobenzene . .
. 0.5 1-Hydroxy-3-aminobenzene . . . 0.1 1-Hydroxy-2-aminobenzene .
. . 0.05 1-Hydroxy-4-aminobenzene . . . 0.09
6-Hydroxybenzomorpholine . . . 0.017
1-b-Hydroxyethyloxy-2,4-diaminobenzene, dihydrochloride 0.039
Propylene glycol monobutyl ether . . . 2.5 Pure monoethanolamine .
. . 1.06 Aqueous ammonia (containing 20.5% of ammonia) . . . 11.1
Water . . . qs . . . 100 AS* = Active Substance
[0372] The dyeing composition was combined, at the time of use, in
a plastic bowl and for 2 minutes, with the oxidizing composition
given above, in an amount of 1 part of dyeing composition per 1.5
parts of oxidizing composition. The mixture obtained was applied to
locks of natural grey hair which is 90% white and allowed to act
for 30 minutes. The locks were then rinsed with water, they were
washed with shampoo and again rinsed with water, and then dried and
disentangled. The hair was then dyed in an intense light chestnut
brown shade.
[0373] Results of the same type were obtained by replacing, in the
above example, Aculyn 44 with 0.5% AS of Quatrisoft LM 200 sold by
the company AMERCHOL or with 0.5% AS of Pure Thix HH sold by the
company SUD CHEMIE.
* * * * *