The present invention relates to a method for permanently reshaping the hair comprising in particular a hair drying step between a step for applying a poorly concentrated reducing composition and a step for applying an oxidizing composition.
Many products are marketed nowadays to easily style, texturize and add some weight to the hair, and especially to thin hair, amongst which foams and styling gels or hair lacquers may be mentioned as an example. These products enable to shape the hair but are removed with shampoo and thus require to be applied on an every day-basis.
The most usual art to obtain a long-lasting deformation of the hair does consist, in a first step, in opening the keratin S-S disulfide bonds (cystine) with a composition comprising a suitable reducing agent (reducing step) then, once the thus treated hair has been rinsed, generally with water, in reforming in a second step said disulfide bonds, by applying onto the hair which has been placed beforehand under tension, using curlers for example, an oxidizing composition (oxidizing step, also called fixing step) so as to give the hair the expected form in the end. These steps are generally conducted by maintaining the keratin fibers under a mechanical stress, for example using curlers.
The new shape that is imposed to the hair by means of a chemical treatment, such as hereabove is temporally substantially long-lasting and does in particular resist to washing operations with water or shampoo, as opposed to the usual simple methods for temporarily reshaping the hair by using foams, styling gels or lacquers.
However, winding up curlers is a technical gesture, that non experienced consumers find difficult to perform. Methods aiming at omitting the step consisting in setting the hair under tension with curlers, so as to control the hair shape have hence been developed.
However, because such methods do not use curlers, they do not provide the hair with a strong tensioning and the hair shape that is thus

obtained using such methods is both rather moderate and relatively shortlived.
As a further drawback, the usual methods to permanently reshape the hair, as described hereabove, which typically require using high contents of thioglycolic acid or a salt thereof, do affect the colour of an artificially coloured hair.
Thus, for example, when such previously described methods for permanently reshaping the hair are applied to hair having beforehand undergone an artificial hair colouring, they cause a degradation or a stripping action on such artificial colour.
No one of the described methods does lead to a fully satisfying permanently reshaping method as regards the hereabove mentioned problems.
Therefore, there is a need for a method for permanently reshaping the hair, that does not affect the artificial hair colour, and that makes it possible to durably perform a hair volume expansion, both at the root level by lifting the same, but also along the whole length. Moreover, this method shall be particularly efficient on short-length and thin hair and provide an improved stylability with an easy to set material.
This need is very perceptible in the field of mass-consumption products.
The applicant discovered that the previously mentioned objectives are aimed at, thanks to a method for permanently reshaping the keratin fibers comprising in particular a keratin fiber drying step between a step for applying a poorly concentrated reducing composition and an oxidation fixing step.
It is thus an object of the invention to provide a method for permanently reshaping the keratin fibers, especially hair keratin fibers, comprising:
- a step for setting the keratin fibers under tension, then
- a step for applying a reducing composition onto the keratin fibers, so
as to reduce the keratin disulfide bonds, said reducing composition
comprising in a cosmetically acceptable medium, from 0.1 to 3% by

weight of at least one reducing agent, as related to the reducing composition total weight, then, after an optional rinsing operation,
- a step for drying the keratin fibers, then
- an oxidation fixing step, so as to reform said bonds, by applying an
oxidizing composition onto the keratin fibers.
Applying onto the keratin fibers a poorly concentrated reducing composition ensures that keratin fibers will be preserved and especially on a coloured hair. In particular, a protecting effect on artificially coloured hair is observed both during the implementation of the method of the invention, and after, upon repeated washing with shampoos. In other words, the method for permanently reshaping the keratin fibers of the invention does not deteriorate the artificial hair colour.
Applying onto the keratin fibers a poorly concentrated reducing composition also enables to carry out the method of the invention many times and temporally at close intervals onto the same keratin fibers, without damaging them, which is not possible with methods employing more concentrated reducing agents.
Applying onto the keratin fibers a poorly concentrated reducing composition further enables to reduce off-odours that are released as compared to the traditional shaping methods.
Applying onto the keratin fibers a poorly concentrated reducing composition finally enables to vary the reaction time on the hair for this composition depending on the hair nature, and does not require to change the reducing composition type depending on the hair type to be treated. The latter point is a strong advantage for the ordinary consumer, as it is not necessary to choose amongst several reducing composition types depending on the nature of the hair, but only to vary its reaction time.
The keratin fiber tensioning step may be performed using any means, such as for example hair elastics, clips, combs, slides, foam rollers or "tulip-type" curlers.

Tulip-type curlers are preferred. They do consist in a body-forming extended rod, ending at one end with a head provided with at least one hole. The curler body is made in a supple and flexible material, so that its free end may be introduced into the head hole and be fixedly maintained there by an elastic clamping. A curler of the hereabove type, particularly suitable for implementing the method of the invention is for example described in the French patent application FR2602650.
Using a tulip-type curler makes it possible to control the tension applied onto the hair and thus to give a rounded form to hair strands during the treatment time, without excessively pulling the hair, as opposed to what happens with most of cylindrical curlers. Tulip-type curlers also have the advantage to be easy to set and to be more comfortable for the scalp, as compared to traditional cylindrical curlers. Depending on the hair shape and on the expected curl volume, the winding up is carried out on more or less thick hair strands.
The method defined hereabove comprises a step for drying the keratin fibers. Drying the keratin fibers may consist in a partial drying or a complete drying, and may be effected for example by means of a domestic hair dryer or a hood hair dryer or a heating hair cap, or the hair may also be let air dry, after it has been carefully wringed out. The keratin fiber drying is preferably a complete drying. A heating device is preferably used to dry the hair.
The reducing composition used in the method of the invention typically comprises, in a cosmetically acceptable medium, at least one reducing agent selected from the group consisting of sulfites, bisulfites, thiols and phosphines.
Suitable examples of sulfites and bisulfites to be used include alkaline metal or alkaline-earth metal, or ammonium sulfites or bisulfites and especially sodium, potassium or monoethanol amine sulfite or bisulfite.
Preferably, the thiol(s) used as reducing agents in the reducing composition is or are selected from the group consisting of cysteine and derivatives thereof, such as N-acetylcysteine, cysteamine and derivatives

thereof, such as C1-C4 acyl derivatives thereof, such as N-acetyl cysteamine and N-propionyl cysteamine, thiolactic acid and esters thereof, such as glycerol monothiolactate, thioglycolic acid and esters thereof, such as glycerol or glycol monothioglycolate, and thioglycerol.
Suitable examples of thiols to be used in the reducing composition used
according to the invention further include sugar N-mercapto alkyl amides,
such as N-(mercapto-2-ethyl)gluconamide, (3-mercaptopropionic acid and
derivatives thereof, thiomalic acid, pantheteine, N-(mercaptoalkyl)co-
hydroxyalkyl amides, such as those described in the European patent
application EP-A-354 835 and N-mono- or N,N-dialkylmercapto 4-
butyramides, such as those described in the European patent application EP-
A-368 763, aminomercaptoalkyl amides, such as those described in the
European patent application EP-A-432 000 and
alkylaminomercaptoalkylamides, such as those described in the European patent application EP-A-514 282, (2/3) hydroxy-2 propyl thioglycolate and hydroxy-2 methyl-1 ethyl thioglycolate-based mixture (67/33) described in the French patent application FR-A-2 679 448.
The applicant demonstrated that applying a cysteine-containing reducing composition enables to obtain a hair volume expansion, both at the root level by lifting the same, but also along the whole hair length, on short-length and thin hair as well.
Most preferably, the reducing composition is selected from the group consisting of L-cysteine, D-cysteine, L,D-cysteine, and their salts, thiolactic acid, salts and esters thereof, thioglycolic acid, salts and esters thereof, and mixtures thereof.
Even more preferably, the reducing agent is cysteine.
The reducing agent(s) preferably represent(s) from 0.3 to 3% by weight, as related to the reducing composition total weight.
According to a preferred embodiment, the reducing composition is allowed to react for 1 to 50 minutes, preferably for 1 to 30 minutes. The

reaction time of the reducing composition will be changed depending on the nature of the hair.
During or after application of the reducing composition, the keratin fibers may be submitted to a thermal treatment by heating, for example to a temperature ranging from 30 to 250°C for part of or all the reaction time defined hereabove. In praxis, this operation may be conducted by means of a hood hair dryer, a hair dryer, a round iron or a flat iron, an IR-emitting device and other heating devices, and in some cases under a plastic film.
The pH value of the reducing composition of the invention does preferably range from 7.5 to 11, preferably from 8 to 9.5.
The pH value of the reducing composition of the invention may be traditionally obtained and/or adjusted by adding either alkaline agents, such as for example ammonia, monoethanol amine, diethanol amine, triethanol amine, isopropanol amine, 2-methyl-2-amino-1-propanol, propanediamine-1,3, alkaline or ammonium carbonate or bicarbonate, sodium carbonate and bicarbonate, an organic carbonate, such as guanidine carbonate, or alkaline hydroxide, where all these compounds may of course be considered either alone or in combination, or acidifying agents, such as for example hydrochloric acid, acetic acid, lactic acid, boric acid, citric acid and phosphoric acid.
For improving the cosmetic properties of the hair fibers or to reduce or prevent their damaging, the reducing composition used in the method of the invention may also comprise one or more cosmetic active agent(s).
This or these active agent(s) is or are generally selected from the group consisting of volatile or non volatile, linear or cyclic, amine-type or not, silicones, cationic, anionic, non ionic or amphoteric polymers, peptides and derivatives thereof, protein hydrolyzates, synthetic or natural waxes, and especially fatty alcohols, swelling agents and penetrating agents or agents intended to improve the efficiency of the reducing agent(s), as well as other active compounds, such as anionic, cationic, non ionic, amphoteric or zwitterionic surfactants, agents for combating hair loss, anti-dandruff agents,

associative-type or not, natural or synthetic thickeners, suspending agents, sequestering agents, opacifying agents, dyes, sunscreen agents, fillers, vitamins or provitamins, mineral, vegetable or synthetic oils, as well as fragrances, preserving agents, stabilizers, and mixtures thereof.
Preferably, the reducing composition comprises a cationic polymer and/or at least one silicone.
As used herein, a "cationic polymer" means any polymer comprising cationic groups or groups ionizable to cationic groups.
Preferred cationic polymers are selected from the group consisting of those which comprise units containing primary, secondary, tertiary and/or quaternary amine groups, that either may belong to the polymer main chain, or be carried by a side substituent that is directly bound to it.
Cationic polymers that are used have generally a number average molecular weight ranging from about 500 to 5.106, and preferably from about 103to3.106.
Cationic polymers more particularly encompass polyamine, polyaminoamide and quaternary polyammonium type polymers.
These are known products. They are in particular described in the French patents n° 2 505 348 or 2 542 997. Said polymers include:
(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of following formulas (I), (II), (III) or (IV):
(Formula Removed)
wherein:
R3, being the same or different, represent a hydrogen atom or a radical;
A, being the same or different, represent a linear or branched alkyl group having from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group having from 1 to 4 carbon atoms;
R4, RS, R0, being the same or different, represent an alkyl group having
from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms;
R1 and R2, being the same or different, represent hydrogen or an alkyl
group having from 1 to 6 carbon atoms and preferably a methyl or an ethyl group;
X represents an anion derived from a mineral or an organic acid, such as a methosulfate anion or a halide, such as chloride or bromide.
Polymers of family (1) may contain in addition one or more unit(s) derived from comonomers that may be selected from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on nitrogen atom with lower (C1-C4)alkyl groups, acrylic or
methacrylic acids or esters thereof, vinyl lactames, such as vinyl pyrrolidone or vinyl caprolactame, and vinyl esters class.
Thus, these polymers of family (1) encompass:
- copolymers of acrylamide and dimethyl aminoethyl methacrylate
quaternized with dimethyl sulfate or dimethyl halide, such as the one
marketed under the name HERCOFLOC by HERCULES,
copolymers of acrylamide and methacryloyloxyethyl trimethylammonium chloride described for example in the European patent application EP-A-080976 and marketed under the name BINA QUAT P 100 by CIBA GEIGY,
- copolymer of acrylamide and methacryloyloxyethyl trimethylammonium
methosulfate marketed under the name RETEN by HERCULES,
- copolymers of vinyl pyrrolidone and dialkylaminoalkyl acrylate or
methacrylate, quaternized or not, such as products marketed under the
name "GAFQUAT" by ISP as for example "GAFQUAT 734" or
"GAFQUAT 755" or products called "COPOLYMER 845, 958 and 937".
These polymers are described in detail in the French patents 2 077 143
and 2 393 573,
- terpolymers of dimethylaminoethyl methacrylate, vinyl caprolactame
and vinyl pyrrolidone, such as the product marketed under the name
GAFFIXVC713bylSP,
- copolymers of vinyl pyrrolidone and methacrylamidopropyl dimethyl
amine marketed in particular under the trade name STYLEZE CC 10 by
ISP,
and quaternized copolymers of vinyl pyrrolidone and dimethylaminopropyl methacrylamide, such as the product marketed under the name "GAFQUAT HS 100" by ISP.
(2) Cellulose ether derivatives comprising quaternary ammonium groups described in the French patent 1 492 597, and especially polymers marketed under the trade names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as being hydroxyethylcellulose quaternary

ammonium compounds having reacted with an epoxide substituted with a trimethylammonium group.
(3) Cationic cellulose derivatives, such as copolymers of cellulose
or cellulose derivatives graft with a quaternary ammonium hydrosoluble
monomer, and described in particular in the American patent US 4,131,576,
such as hydroxyalkyl celluloses, as for example hydroxymethyl-,
hydroxyethyl- or hydroxypropyl celluloses graft in particular with a
methacryloylethyl trimethylammonium, methacrylmidopropyl
trimethylammonium, or a dimethyl diallylammonium salt.
The products marketed corresponding to this definition are more particularly products marketed under the name "Celquat L 200" and "Celquat H 100" by National Starch.
(4) Cationic polysaccharides described more particularly in the
American patents US 3,589,578 and 4,031,307, such as guar gums
containing trialkylammonium cationic groups. Guar gums modified with a 2,3-
epoxypropyl trimethylammonium (par ex. chloride) salt are used for example.
Such products are marketed in particular under the trade names JAGUAR C13S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by MEYHALL.
(5) Polymers consisting in piperazinyl units and alkylene or
hydroxyalkylene divalent radicals with straight or branched chains, optionally
interrupted with oxygen, sulfur, nitrogen atoms or with aromatic or
heterocyclic rings, as well as oxidation products and/or quaternization
products of these polymers. Such polymers are in particular described in the
French patents 2 162 025 and 2 280 361.
(6) Water-soluble polyaminoamides especially prepared by
polycondensing an acidic compound with a polyamine; these

polyaminoamides may be crosslinked with a epihalohydrine, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrine, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or with an oligomer resulting from the reaction of a bifunctional compound reactive against a bis-halohydrine, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydrine, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in amounts ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides may be alkylated or, in the event they have one or more tertiary amine function(s), quaternized. Such polymers are in particular described in the French patents 2 252 840 and 2 368 508.
(7) Polyaminoamides derivatives resulting from the condensation of
polyalkylene polyamines with des polycarboxylic acids, followed with an
alkylation with bifunctional agents. Polymers of adipic acid and
dialkylaminohydroxyalkyl dialkylene triamine may be mentioned for example,
wherein the alkyl radical contains from 1 to 4 carbon atoms and represents
preferably a methyl, an ethyl or a propyl. Such polymers are in particular
described in the French patent 1 583 363.
Amongst these derivatives, polymers of adipic acid, dimethylaminohydroxypropyl and diethylene triamine marketed under the name "Cartaretine F, F4 or F8" by Sandoz may be more particularly described.
(8) Polymers obtained by reacting a polyalkylene polyamine
comprising two primary amine groups and at least one secondary amine
group with a dicarboxylic acid selected from diglycolic acid and saturated
aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio
of the polyalkylene polyamine to the dicarboxylic acid ranging from 0.8:1 to
1.4:1; the thus resulting polyaminoamide being reacted with epichlorhydrine
according to a molar ratio of epichlorhydrine to secondary amine group of the

polyaminoamide ranging from 0.5:1 to 1,8:1. Such polymers are in particular described in the American patents 3,227,615 and 2,961,347.
Polymers of this type are especially marketed under the trade name "Hercosett 57" by Hercules Inc. or under the trade name "PD 170" or "Delsette 101" by Hercules in the case of the copolymer of adipic acid, epoxypropyl and diethylene triamine.
(9) Cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium, such as homopolymers or copolymers comprising as a main substituent of the chain units of formulas (V) or (VI):
(Formula Removed)
wherein k and t are 0 or 1, the sum k + t being equal to 1; R7 represents a hydrogen atom or a methyl radical; R7 and R8, independently from each
other, represent an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group wherein the alkyl group preferably contains from 1 to 5 carbon atoms, a lower amido(C1-C4)alkyl group, or R7 and R8 may
represent together with the nitrogen atom to which they are bound, heterocyclic groups, such as piperidinyl or morpholinyl; R¬7 and R8
independently from each other preferably represent an alkyl group having

from 1 to 4 carbon atoms; Y" is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are in particular described in the French patent 2 080 759 and in its patent of addition N° 2 190 406.
The previously defined polymers also encompass more particularly the dimethyldiallylammonium chloride homopolymer marketed under the name "Merquat 100" by Calgon (as well as its homologues having a low weight average molecular weight) and copolymers of diallyldimethylammonium chloride and acrylamide marketed under the trade name "MERQUAT 550".
(10) the diquaternary ammonium polymer containing repeating units of following formula (VII):
(Formula Removed)
wherein:
R10 R11 Rl2 and R13 being the same or different, represent aliphatic, alicyclic, or aryl aliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkyl aliphatic radicals, or R10, R11, R12 and R13, taken
together or separately, form together with the nitrogen atoms to which they are bound heterocycles optionally containing a second heteroatom different from nitrogen or R10, R11, R12 and R13 represent a linear or branched, C1-C4 alkyl radical, substituted with a nitrite, ester, acyl, amide or -CO-O- R14-D or -CO-NH- R14-D group, where R14 is an alkylene and D a quaternary
ammonium group;
A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms that may be linear or branched, saturated or unsaturated, and that may contain, bound to or inserted within the main chain, one or more aromatic rings, or one or more oxygen or sulfur atom(s), or sulfoxide, sulfone,

disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
X" represents an anion derived from a mineral or an organic acid;
A1, R10, R11, R12 and R13 together with the two nitrogen atoms to which they are bound a piperazine ring; moreover, if A1 represents a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also represent a -(CH2)n-CO-D-OC-(CH2)n- group, wherein D
represents:
a) a glycol residue of formula: -0-Z-0-, where Z represents a
linear or branched hydrocarbon radical or a group having one of the following
formulas:
-(CH2-CH2-O)x-CH2-CH2--[CH2-CH(CH3)-0]y-CH2-CH(CH3)-
wherein x and y represent an integer from 1 to 4, corresponding to a defined and unique polymerization degree, or any number from 1 to 4 corresponding to a medium polymerization degree;
b) a bis-secondary diamine residue, such as a piperazine
derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-,
wherein Y represents a linear or branched hydrocarbon radical, or the
bivalent radical
-CH2-CH2-S-S-CH2-CH2-;
d) a ureylene group of formula: -NH-CO-NH-.
Preferably, X" is an anion, such as chloride or bromide.
These polymers have a number average molecular weight generally ranging from 1000 to 100000.
Such polymers are in particular described in the French patents 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 as well as in the American patents US 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.
More particularly, such polymers may be used, that do comprise repeating units of following formula (VIII):
(Formula Removed)wherein R10, R11, R12 and R13, being the same or different, represent an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms
approximately, n and p are integers ranging from about 2 to 20 and X~ is an anion derived from a mineral or an organic acid. Hexadimethrine chloride (INCI name), marketed by CHIMEX under the reference MEXOMERE POLYMERE D'OLEFIN may be especially mentioned;
(11) Quaternary polyammonium compounds comprising repeating units of formula (IX):
CH3 * X" CH3
-N - (CH2)p-NH-CO-D-NH- (CH2)p - N - (CH2)2 - O - (CH2)2 -|- (IX)
CH3 CH3
wherein p represents an integer ranging from about 1 to 6, D may be zero or may represent a -(CH2)r -CO- group, wherein r represents a number equal to
4 or 7, X~ is an anion;
Such polymers may be prepared according to methods described in the American patents n° 4,157,388, 4,702,906, 4,719,282. They are in particular described in the European patent application EP-A-122 324.
Suitable examples thereof are "Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175" products sold by Miranol.

(12) Quaternary polymers of vinyl pyrrolidone and vinyl imidazole,
such as for example the products marketed under the trade names Luviquat
FC 905, FC 550 and FC 370 by BASF.
(13) Polyamines, such as Polyquart H sold by HENKEL, under the
reference "POLYETHYLENE GLYCOL (15) TALLOW POLYAMINE" in the
CTFA dictionary.
(14) Crosslinked polymers of methacryloyloxyalkyl(C-|-C4) trialkyl(C1-
C4)ammonium salts, such as polymers obtained by homopolymerizing the
dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerizing the acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, where the homo- or copolymerization are followed with a crosslinking with an olefinically unsaturated compound, especially methylene bis acrylamide. A crosslinked copolymer of acrylamide and methacryloyloxyethyl trimethylammonium chloride (20:80 by weight) may be especially used in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. Such dispersion is marketed under the trade
name "SALCARE® SC 92" by ALLIED COLLOIDS. A crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride may also be used, containing about 50% by weight of said homopolymer in mineral oil or in a liquid ester. Such dispersions are marketed under the trade names
"SALCARE® SC 95" and "SALCARE® SC 96" by ALLIED COLLOIDS.
Other cationic polymers to be suitably used in the context of the present invention are polyalkylene imines, especially polyethylene imines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrine, quaternary polyureylenes and chitin derivatives.

Amongst all the cationic polymers that might be used in the context of the present invention, it is preferred to employ a cationic polymer belonging to family (10) and for example hexadimethrine chloride (INCI name), marketed by CHIMEX under the reference MEXOMERE PO.
The cationic polymer content in the composition of the invention may vary from 0.01 to 10% by weight as related to the composition total weight, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.
As previously explained, the cosmetic active agent(s) that may be used in the composition of the invention may also be selected from the group consisting of silicones.
Silicones that are optionally present in the reducing composition of the invention are especially polyorganosiloxanes which are not soluble in said composition and may come as oils, waxes, resins or gums.
Organopolysiloxanes are defined in more detail by Walter NOLL in "Chemistry and Technology of Silicones" (1968) Academic Press.
Silicones may be volatile or not.
When they are volatile, silicones are more particularly selected from those having a boiling point ranging from 60° C to 260° C, and even more particularly from the following ones:
(i) cyclic silicones comprising from 3 to 7 silicon atoms and preferably 4 or 5.
Suitable examples thereof include octamethylcyclotetrasiloxane marketed in particular under the trade name "VOLATILE SILICONE 7207" by UNION CARBIDE or "SILBIONE 70045 V 2" by RHONE POULENC, decamethylcyclopentasiloxane marketed under the trade name "VOLATILE SILICONE 7158" by UNION CARBIDE, "SILBIONE 70045 V 5" by RHONE POULENC, as well as mixtures thereof.
Cyclocopolymers of the dimethyl siloxane and methylalkyl siloxane type may also be mentioned, such as "SILICONE VOLATILE FZ 3109" marketed by UNION CARBIDE, having following chemical structure (X):

(Formula Removed)
Mixtures of cyclic silicones with organic compounds derived from silicon may also be mentioned, such as the octamethyl cyclotetrasiloxane and tetratrimethylsilyl pentaerythritol mixture (50:50) and the octamethyl cyclotetrasiloxane and oxy-I’Xhexa2’2’2’2’3’3’
trimethylsilyloxy) bis-neopentane mixture;
(ii) linear volatile silicones having from 2 to 9 silicon atoms and which viscosity is lower than or equal to 5.10-6m2/s at 25° C, as for example decamethyl tetrasiloxane marketed in particular under the trade name "SH 200" by TORAY SILICONE. Silicones belonging to this class are also described in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, P. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics".
Non volatile silicones are preferably used and more particularly polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, gums and silicone resins, polyorganosiloxanes modified with organofunctional groups as well as mixtures thereof.
These silicones are more particularly selected from polyalkyl siloxanes, from which polydimethyl siloxanes with trimethylsilyl end groups may be especially mentioned having a viscosity ranging from 5.10-6to 2.5 m2/s at 25°C and preferably from 1.10"5 to 1 m2/s. Silicone viscosity is for example measured at 25°C according to ASTM 445 standard, Appendix C.
These polyalkyl siloxanes encompass, as non limitative examples, the following commercial products:
- SILBIONE fluids of 47 and 70 047 series or MIRASIL fluids marketed
by RHONE POULENC, such as for example fluid 70 047 V 500 000;
- fluids of MIRASIL series marketed by RHONE POULENC;

- fluids of 200 series from DOW CORNING, especially, such as
DC200 (viscosity 60 000 Cst);
- VISCASIL fluids from GENERAL ELECTRIC and some fluids of SF
(SF 96, SF 18) series from GENERAL ELECTRIC.
Dimethylsilanol end group-containing polydimethyl siloxanes may also
be mentioned (called dimethiconol in the CTFA dictionary), such as fluids of 48 series from RHONE POULENC.
This polyalkyl siloxane class also includes products marketed under the trade names "ABIL WAX 9800 and 9801" by GOLDSCHMIDT which are (C1-C2o) polyalkyl siloxanes.
Polyalkylaryl siloxanes are especially selected from the group consisting of linear and/or branched, polydimethyl methylphenyl siloxanes, or polydimethyl diphenyl siloxanes with a viscosity ranging from 1.10-5 to 5.10" 2m2/s at 25°C.
Suitable examples of such polyalkylaryl siloxanes also include products marketed under the following trade names:
. SILBIONE fluids of 70 641 series from RHONE POULENC;
. fluids of RHODORSIL 70 633 and 763 series from RHONE
POULENC;
. DOW CORNING 556 COSMETIC GRAD FLUID from DOW
CORNING;
. silicones of PK series from BAYER, such as the PK20 product;
. silicones of PN, PH series from BAYER, such as PN1000 and
PH1000 products;
. some fluids of SF series from GENERAL ELECTRIC, such as SF 1023, SF 1154, SF 1250, SF 1265.
Silicone gums that may be present in the reducing composition of the invention are in particular polydiorganosiloxanes having high number average molecular weights ranging from 200 000 to 1 000 000 used either alone or in combination in a solvent. This solvent may be selected from the group consisting of volatile silicones, polydimethyl siloxanes fluids (PDMS),
polyphenylmethyl siloxane fluids (PPMS), isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecanes or mixtures thereof. Following products may in particular be mentioned:
- polydimethyl siloxane,
- polydimethyl siloxane /methylvinyl siloxane gums,
- polydimethyl siloxane /diphenyl siloxane,
- polydimethyl siloxane /phenylmethyl siloxane,
- polydimethyl siloxane /diphenyl siloxane /methylvinyl siloxane.
Products to be used more particularly are following mixtures:

- mixtures formed from end chain-hydroxylated polydimethyl siloxane
(called dimethiconol according to the CTFA dictionary nomenclature) and
cyclic polydimethyl siloxane (called cyclomethicone according to the CTFA
dictionary nomenclature), such as the Q2 1401 product marketed by DOW
CORNING;
- mixtures formed from polydimethyl siloxane gum and cyclic silicone,
such as the SF 1214 Silicone Fluid from GENERAL ELECTRIC product, this
one being a SF 30 gum corresponding to a dimethicone, having a number
average molecular weight of 500 000 solubilized in fluid SF 1202 Silicone
Fluid corresponding to decamethyl cyclopentasiloxane;
- mixtures from two PDMS with different viscosities, and more
particularly from a PDMS gum and a PDMS fluid, such as the SF 1236
product from GENERAL ELECTRIC. SF 1236 is a mixture from a SE 30 gum
as defined hereabove with a viscosity of 20 m2/s and a SF 96 fluid with a
viscosity of 5.10"6m2/s. Such product comprises preferably 15% of SE 30
gum and 85% of SF 96 fluid.
Organopolysiloxane resins optionally present in the oxidizing composition of the method of the invention are siloxane-based crosslinked systems comprising following units: R2SiO2/2, R3SiO1/2, RSiO3/2 and Si04/2, wherein R represents a hydrocarbon group having from 1 to 16 carbon atoms or a phenyl group. Amongst these products, those particularly preferred are
those wherein R represents a lower C1-C4 alkyl radical, more particularly a methyl or a phenyl radical.
These resins also include the product marketed under the trade name "DOW CORNING 593" or those marketed under the trade names "SILICONE FLUID SS 4230 and SS 4267" by GENERAL ELECTRIC and which are dimethyl/trimethyl siloxane-structured silicones.
Resins of the trimethyl siloxysilicate type marketed in particular under the trade names X22-4914, X21-5034 and X21-5037 by SHIN-ETSU may also be mentioned.
Organomodified silicones optionally present in the reducing composition of the invention are silicones, such as previously defined and comprising in their structure one or more organofunctional group(s) bound by means of a hydrocarbon radical.
Organomodified silicones include polyorganosiloxanes comprising:
- polyethyleneoxy and/or polypropyleneoxy groups optionally
comprising C2-C24 alkyl groups, such as products called dimethicone copolyol
marketed by DOW CORNING under the trade name DC 1248 or SILWET L
722, L 7500, L 77, L 711 fluids from UNION CARBIDE and (C12)alkyl
methicone copolyol marketed by DOW CORNING under the trade name C2
5200;
- amine groups, substituted or not, such as the products marketed
under the trade name GP 4 Silicone Fluid and GP 7100 by GENESEE, the
176-12096G products from GENERAL ELECTRIC, the KF-860, 861 and 864
products from SHINETSU or the products marketed under the trade names
02 8220 or DCZ-8566 and DOW CORNING 929 or 939 or DCZ-8299 or
QZ7224 by DOW CORNING. Substituted amine groups are especially C1-C4
aminoalkyl groups; amino silicones comprising alkoxy groups, such as
BELSIL ADM LOG 1 silicone marketed by WACKER;
- thiol groups, such as the products marketed under the trade names
"GP 72 A" and "GP 71" from GENESEE;
- alkoxyl groups, such as the product marketed under the trade name
"SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX 2428,
2434 and 2440 by GOLDSCHMIDT;
- hydroxyl groups, such as hydroxyalkyl function-containing
polyorganosiloxanes described in the French patent application FR-A-85
16334;
- acyloxyalkyl groups, such as for example polyorganosiloxanes
described in the American patent US-A-4957732;
- anionic groups of the carboxylic type as for example in the products
described in the European patent EP 186 507 from CHISSO
CORPORATION, or of the alkyl carboxylic type, such as those present in the
X-22-3701E product from SHIN-ETSU; 2-hydroxyalkyl sulfonate; 2-
hydroxyalkyl thiosulfate, such as products marketed by GOLDSCHMIDT
under the trade names "ABIL S201" and "ABIL S255";
- hydroxyacylamino groups, such as polyorganosiloxanes described in
the European application EP 342 834, as for example the Q2-8413 product
from DOW CORNING.
The silicone is preferably an amino silicone.
As previously explained, the method of the invention comprises an oxidizing composition applying step.
The oxidizing composition comprises generally at least one oxidizing agent selected from the group consisting of hydrogen peroxide, carbamide peroxide, alkaline bromates, polythionates, persalts, such as perborates, percarbonates and persulfates.
The oxidizing agent is preferably hydrogen peroxide.
The oxidizing agent(s) represent(s) generally from 0.1 to 10%, preferably from 0.5 to 5% by weight as related to the oxidizing composition total weight.
Preferably, when the oxidizing agent represents hydrogen peroxide in aqueous solution, the oxidizing composition used in the method of the invention contains at least one hydrogen peroxide stabilizing agent.

Alkaline metal or alkaline-earth metal pyrophosphates, such as tetrasodium pyrophosphate, alkaline metal or alkaline-earth metal stannates, phenacetine or acid and oxyquinoline salts, such as oxyquinoline sulfate. Even more advantageously, at least one stannate is used in combination, or not, with at least one pyrophosphate.
The hydrogen peroxide stabilizing agent(s) do(es) typically represent from 0.0001% to 5% by weight and preferably from 0.01 to 2% by weight as related to the oxidizing composition total weight.
To improve the cosmetic properties of the hair fibers or to reduce or prevent their damaging, the oxidizing composition used in the method of the invention may also comprise one or more cosmetic active agent(s), such as those previously mentioned with respect to the reducing composition.
Typically, the pH value of the oxidizing composition does vary from 1.5 to 4.5, preferably from 2 to 3.5.
Preferably, the oxidizing composition is allowed to react for 2 to 30 minutes, preferably for 2 to 15 minutes, more preferably from 2 to 7minut.es.
Preferably, the method of the invention comprises a step for applying a hair-care composition containing a cationic polymer.
All the cationic polymers that have been described hereabove as regards the reducing composition may be used in the hair-care composition.
Amongst all cationic polymers that might be used in the context of the present invention, it is preferred to include in the reducing composition cyclopolymers, especially dimethyldiallylammonium chloride homopolymers marketed under the trade name "MERQUAT® 100" by MERCK, diquaternary ammonium polymers of formula (VIII) or of formula (IX) and especially MEXOMERE PO.
WACKER BELSIL ADM LOG 1 silicone is the most preferred silicone.
A step for applying a hair-care composition enables to limit or to prevent sensibilizing the hair which could result from the hair treatment by the reducing agents and the oxidizing agents during the process for permanently

reshaping the hair according to the invention. The hair-care composition, such as defined hereabove also enables to protect the hair artificial colour.
The oxidizing composition and the hair-care composition used in the method of the invention may also comprise one or more cosmetic active agent(s), such as those previously mentioned with respect to the reducing composition.
The vehicle for the reducing, oxidizing and hair-care compositions used in the method of the invention is preferably an aqueous medium consisting in water and may advantageously contain some cosmetically acceptable organic solvents, which more particularly include alcohols, such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or polyols or polyol ethers, such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, such as, for example, propylene glycol monomethylether, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl ethers, such as for example, diethylene glycol monoethylether or monobutylether. Organic solvents may then be present in concentrations ranging from about 0.1 to 20% and, preferably from about 1 to 10% by weight as related to the composition total weight.
The pH value of the reducing composition, the oxidizing composition and the hair-care composition used in the method of the invention may be obtained and/or adjusted traditionally by adding either alkaline agents, such as for example ammonia, monoethanol amine, diethanol amine, triethanol amine, isopropanol amine, 2-methyl-2-amino-1-propanol, propanediamine-1,3, alkaline or ammonium carbonate or bicarbonate, organic carbonate, such as guanidine carbonate, or alkaline hydroxide, where all these compounds may of course be considered either alone or in combination, or acidifying agents, such as for example hydrochloric acid, acetic acid, lactic acid, boric acid, citric acid and phosphoric acid.
The reducing composition, the oxidizing composition and the hair-care composition used in the method of the invention may present independently

from each other in the form of a lotion, a gel, thickened or not, a foam, or a cream.
The method of the invention may comprise a step for applying a composition comprising a fixing polymer, preferably between the step for setting the keratin fibers under mechanical tension and the step for applying the reducing composition.
To use the immediately hereabove defined composition, it is theoretically possible to use any natural or synthetic fixing polymer giving a form to the hair or changing said hair form. Preferably, the fixing polymer used is anionic or amphoteric in nature; mixtures of anionic and amphoteric polymers may also be used.
Anionic polymers that are generally used are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids, and having a weight average molecular weight ranging from 500 to 5 000 000.
Carboxylic groups are brought by unsaturated carboxylic monoacid or diacid monomers, such as those of following formula (XI):
(Formula Removed)
wherein n is an integer from 0 to 10, A represents a methylene group, optionally bound to the carbon atom of the unsaturated group or to the adjacent methylene group when n is higher than 1, by means of a heteroatom, such as oxygen or sulfur, R1 represents a hydrogen atom, a phenyl or benzyl group, R2 represents a hydrogen atom, a lower alkyl group or a carboxyl group, R3 represents a hydrogen atom, a lower alkyl group, a -CH2-COOH, phenyl or benzyl group.
In formula (XI) hereabove, a lower alkyl group preferably comprises from 1 to 4 carbon atoms and represents in particular, methyl and ethyl groups.
Hereunder are preferred carboxylic or sulfonic group-containing anionic polymers:
A) homo- or copolymers of acrylic or methacrylic acid or their salts,
including copolymers of acrylic acid and acrylamide and copolymers of
methacrylic acid, acrylic acid, ethyl acrylate/methyl methacrylate, especially
AMERHOLD DR 25 marketed by AMERCHOL, and polyhydroxycarboxylic
acid sodium salts. Copolymers of methacrylic acid and ethyl acrylate, in
particular in aqueous dispersion, such as LUVIFLEX SOFT and LUVIMER
MAE marketed by BASF may also be mentioned.
B) copolymers of acrylic or methacrylic acids with a monoethylene
monomer, such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid
esters, which are optionally graft on polyalkylene glycol, such as polyethylene
glycol, and optionally crosslinked. Such polymers are described especially in
the French patent 1 222 944 and in the German application n° 2 330 956,
copolymers of this type comprising in their chain an optionally N-alkylated
and/or hydroxyalkylated acrylamide unit, such as described in particular in
the Luxemburger patent applications 75370 and 75371. Copolymers of
acrylic acid and C1-C4 alkyl methacrylate may also be mentioned.
C) copolymers derived from crotonic acid, such as those comprising in
their chain vinyl acetate or propionate units, and optionally other monomers,
such as alkyl or methyl ester, vinyl ether or vinyl ester of a saturated, linear
or branched, hydrocarbon long-chain carboxylic acid, such as those
comprising at least 5 carbon atoms, where these polymers may optionally be
graft and crosslinked, or a vinyl, alkyl or methyl ester of a cyclic a- or p-
carboxylic acid. Such polymers are described inter alia in the French patents
n° 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2 439 798.
Commercial products belonging to this class are the 28-29-30, 26-13-14 and
28-13-10 resins sold by NATIONAL STARCH.
As an example of a copolymer derived from crotonic acid, terpolymers of crotonic acid/ vinyl acetate/ vinyl tertbutylbenzoate and especially MEXOMERE PW marketed by CHIMEX may also be mentioned.
D) polymers derived from maleic, fumaric, itaconic acids or anhydrides
with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic
acid and esters thereof; these polymers may be esterified. Such polymers
are described especially in the American patents US 2,047,398, 2,723,248,
2,102,113, the British patent 839 805, and in particular those sold under the
trade names GANTREZ® AN or ES by ISP.
Polymers also belonging to such class are copolymers of maleic, citraconic, itaconic anhydrides with an alkyl or methallyl ester optionally comprising an acrylamide or methacrylamide group, an a-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinyl pyrrolidone in their chain, anhydride functions being monoesterified or monoamidified. These polymers are for example described in the French patents 2 350 384 and 2 357241 of the applicant.
E) polyacrylamides comprising carboxylate groups.
F) polymers comprising sulfonic groups. These polymers may be
polymers comprising vinyl sulfonic, styrene sulfonic, naphthalene sulfonic,
acrylamido alkyl sulfonic, sulfoisophthalate units.
These polymers may be in particular selected from:
- polyvinyl sulfonic acid salts having a molecular weight ranging from
about 1 000 to 100 000, as well as copolymers with an unsaturated
comonomer, such as acrylic or methacrylic acids, and esters thereof, as well
as acrylamide or derivatives thereof, vinyl ethers and vinyl pyrrolidone;
- polystyrene sulfonic acid salts, sodium salts, having a molecular
weight ranging from about 500 000 to about 100 000. These compounds are
described in the French patent FR 2198719;
- polyacrylamide sulfonic acid salts, such as those mentioned in the
American patent US 4,128,631;
G) silicone anionic graft polymers;
Silicone graft polymers used are preferably selected from the group consisting of polymers with an organic non silicone backbone, graft with
polysiloxane-containing monomers, polysiloxane backbone polymers graft with non silicone organic monomers and mixtures thereof.
All along the following or preceding description, a silicone or a polysiloxane is intended to mean in accordance with the generally accepted definition, any organosiliced oligomer polymer with a linear or cyclic, branched or crosslinked structure, having a varying molecular weight, obtained by polymerizing and/or polycondensing suitably functionalized silanes, and substantially consisting in repeating main units, wherein silicon atoms are bound to each other with oxygen atoms (siloxane bond =Si-0-Si=), optionally substituted hydrocarbon radicals being directly bound by means of a carbon atom on said silicon atoms. Most frequent hydrocarbon radicals are alkyl radicals in particular C1-C10 alkyl radicals and especially methyl, fluoralkyl radicals, aryl radicals and especially phenyl, and alkenyl radicals and especially vinyl; other types of radicals that might be bound either directly, or by means of a hydrocarbon radical, to the siloxane chain are in particular hydrogen, halogens and especially chlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene radicals (or polyethers) and especially polyoxyethylene and/or polyoxypropylene, hydroxyl or hydroxyalkyl radicals, substituted or not substituted amine groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals, quaternary ammonium groups, amphoteric or betaine groups, anionic groups, such as carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates, this list being of course absolutely not limitative (silicones that are said to be "organomodified").
As used herein, a "polysiloxane macromer" in accordance with the generally accepted definition is intended to mean any monomer containing in its structure a polysiloxane type polymer chain.
Polymers with an organic non silicone backbone, graft with polysiloxane-containing monomers, used according to the present invention do consist in an organic main chain formed from organic monomers that do

not contain any silicone, onto which at least one polysiloxane macromer has been graft within said chain, as well as optionally to at least one end thereof.
The non silicone organic monomers forming the main chain of the silicone graft polymer may be selected from ethylenically unsaturated free-radical polymerizable monomers, polycondensation polymerizable monomers, such as those forming polyamides, polyesters, polyurethanes, open-ring monomers, such as those of the oxazoline or caprolactone type.
Polymers with an organic non silicone backbone, graft with polysiloxane-containing monomers to be used may be obtained according to any means known by the man skilled in the art, especially by reacting (i) an initial polysiloxane macromer suitably functionalized on the polysiloxane chain with (ii) one or more non silicone organic compound(s), that are in turn suitably functionalized with a function that can react with the functional group(s) carried on said silicone by forming a covalent bond; a usual example of such a reaction being the radical reaction between a vinyl group carried on one of the silicone ends with a double bond of an ethylenically unsaturated monomer of the main chain.
The polymers with an organic non silicone backbone, graft with polysiloxane-containing monomers, according to the invention, are more preferably selected from those described in the American patents US 4,693,935, US 4,728,571 and US 4,972,037 and in the patent applications EP-A-0412704, EP-A-0412707, EP-A-0640105 and WO 95/00578. They are copolymers obtained by means of a radical polymerization from ethylenically unsaturated monomers and silicone macromers having a vinyl end group or copolymers obtained by reacting a polyolefin comprising functionalized groups with a polysiloxane macromer having an end function reactive with said functionalized groups.
A particular silicone graft polymer family that may be suitably used for implementing the present invention comprises silicone graft copolymers comprising:

a) from 0 to 98% by weight of at least one lipophilic, ethylenically
unsaturated, free-radical polymerizable (A1) monomer having a low polarity;
b) from 1 to 98% by weight of at least one hydrophilic, polar,
ethylenically unsaturated monomer (B1) copolymerizable with the monomer(s)
of type (A);
c) from 0.01 to 50% by weight of at least one polysiloxane macromer
(C1) of general formula (XII):
(Formula Removed)
Wherein:
X represents a vinyl group copolymerizable with monomers (A1) and (B');
Y represents a divalent linkage group;
R represents a hydrogen atom, a C1-C6 -alkyl or -alkoxy group, a C6-C12 aryl group;
Z represents a monovalent polysiloxane unit having a number average molecular weight of at least 500;
n is 0 or 1 and m is an integer ranging from 1 to 3; percentages being calculated as related to the total weight of (A1), (B') and (C1).
The polymers, and their preparation methods as well, are described in the American patents US 4,963,935, US 4,728,571 and US 4,972,037 and in the European patent applications EP-A-0412704, EP-A-0412707, EP-A-0640105. They have a number average molecular weight preferably ranging from 10 000 to 2 000 000 and preferably a glass transition temperature Tg or a crystalline melting point Tm of at least -20°C.
Suitable examples of lipophilic monomers (A1) include C1-C18 alcohol acrylic or methacrylic acid esters; styrene; polystyrene macromers; vinyl acetate; vinyl propionate; alpha-methylstyrene; tertio-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyltoluene; esters of acrylic or methacrylic acid and of 1,1-dihydroperfluoroalkanol or homologues thereof;

esters of acrylic or methacrylic acid and omega-hydrydofluoroalkanol; esters of acrylic or methacrylic acid and fluoroalkylsulfoamido alcohol; esters of acrylic or methacrylic acid and fluoroalkyl alcohol; esters of acrylic or methacrylic acid and alcohol fluoroether; or mixtures thereof.
Preferred monomers (A1) are selected from the group consisting of n-
butyl methacrylate, isobutyl methacrylate, tertio-butyl acrylate, tertio-butyl
methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, 2-(N-methyl
perfluoroctane sulfoamido)ethylacrylate; 2-(N-butylperflurooctane
sulfoamido)ethylacrylate and mixtures thereof.
Suitable examples of polar monomers (B1) include acrylic acid, methacrylic acid, N,N-dimethylacryl amide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, (meth)acrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride and their half-esters, hydroxyalkylated (meth)acrylates, diallyldimethylammonium chloride, vinyl pyrrolidone, vinyl ethers, maleimides, vinyl pyridine, vinyl imidazole, heterocyclic vinyl polar compounds, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactame or mixtures thereof. Preferred monomers (B1) are selected from the group consisting of acrylic acid, N,N-dimethylacryl amide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone and mixtures thereof.
As polar monomers (B')? anionic silicone graft polymers used according to the invention comprise at least one anionic monomer.
Preferred polysiloxane macromers (C1) of formula (XII) are selected from the group consisting of those of following general formula (XIII):
(Formula Removed)
wherein:
R1 represents hydrogen or-COOH (preferably hydrogen);
R2 represents hydrogen, a methyl group or -CH2COOH (preferably a methyl group);
R3 is a C1-C6 alkyl, alkoxy or alkylamino group, a C1-C12 aryl group or a hydroxyl group (preferably a methyl group);
R4 is a C1-C6 alkyl, alkoxy or alkylamino group, a C1-C12 aryl group or a hydroxyl group (preferably a methyl group);
q is an integer from 2 to 6 (preferably 3);
p is 0 or 1;
r is an integer ranging from 5 to 700;
m is an integer ranging from 1 to 3 (preferably 1);
More particularly polysiloxane macromers of following formula are used:
(Formula Removed)
n being an integer ranging from 5 to 700.
A particular embodiment of the invention consists in using a copolymer that may be obtained by free-radical polymerization from a mixture of monomers comprising:
60% by weight of tertiobutyl acrylate:
20% by weight of acrylic acid;
20% by weight of silicone macromer of formula:
(Formula Removed)
n being an integer ranging from 5 to 700; percentages by weight being calculated as related to the monomer total weight.
Another particular silicone polymer family suitable for implementing the present invention includes silicone graft copolymers that may be obtained by reactive extrusion of a polysiloxane macromer having a reactive end function on a polyolefin-type polymer comprising reactive groups that may react with the end function of the polysiloxane macromer to form a covalent bond enabling grafting the silicone on the polyolefin main chain.
These polymers, as well as their preparation methods, are described in the patent application WO 95/00578.
Reactive polyolefins are preferably selected from the group consisting of polyethylenes or polymers of monomers derived from ethylene, such as propylene, styrene, alkyl styrenes, butylene, butadiene, (meth)acrylates, vinyl esters or equivalents, comprising reactive functions that may react with the end function of the polysiloxane macromer. They are more particularly selected from copolymers of ethylene or ethylene derivatives and of monomers selected from those comprising a carboxylic function, such as (meth)acrylic acid; those comprising an acid anhydride function, such as maleic acid anhydride; those comprising an acid chloride function, such as (meth)acrylic acid chloride; those comprising an ester function, such as (meth)acrylic acid esters; those comprising an isocyanate function.
Silicone macromers are preferably selected from polysiloxanes comprising a functionalized group, at the end of the polysiloxane chain or close to the end of said chain, selected from the group consisting of alcohols, thiols, epoxy, primary and secondary amines and more particularly from those of following general formula (XVI):

(Formula Removed)
wherein T is selected from the group consisting of NH2, NHR', an epoxy function, OH, SH; R5, R6, R7 and R8, independently, represent a C1-C6 alkyl group, a phenyl, a benzyl, or a C6-C12 alkyl phenyl group, hydrogen; s is a number ranging from 2 to 100; t is a number ranging from 0 to 1000 and y is a number ranging from 1 to 3. They have a number average molecular weight preferably ranging from 5 000 to 300 000, more preferably from 8 000 to 200 000 and even more particularly from 9 000 to 40 000.
According to the present invention, the graft silicone polymer(s) having a polysiloxane backbone graft with non silicone organic monomers comprise a silicone main chain (or polysiloxane (=Si-0-)n), on which at least one organic group free from silicone has been graft within said chain as well as optionally to at least one end thereof.
Polysiloxane backbone polymers graft with non silicone organic monomers according to the invention may be existing commercial products or they also may be obtained according to any means known by the man skilled in the art, especially by making (i) a starting silicone suitably functionalized on one or more of its silicon atoms react with (ii) a non-silicone organic compound itself suitably functionalized with a function that can react with the functional group(s) carried on said silicone by forming a covalent bond; a usual example of such a reaction is the hydrosylilation reaction between =Si-H groups and CH2=CH- vinyl groups, or the reaction between -SH thio-functional groups with said vinyl groups.
Examples of polysiloxane backbone polymers graft with non silicone organic monomers that may suitably be used for implementing the present invention, as well as their particular preparation procedure, are in particular described in the patent applications EP-A-0582152, WO 93/23009 and WO 95/03776, the teaching of which is incorporated herein in its enterity as a non limitative reference.

According to a particularly preferred embodiment of the present invention, the polysiloxane backbone silicone polymer, graft with non silicone organic monomers, that is used comprises the result of a radical copolymerization between, on the one hand, at least one ethylenically unsaturated, organic anionic non-silicone monomer and/or anethylenically unsaturated organic hydrophobic non-silicone monomer and on the other hand, a silicone that does contain in its chain at least one functional group that can be reacted with said ethylenic unsaturations of said non-silicone monomers by forming a covalent bond, especially thio-functional groups.
According to the present invention, said anionic ethylenically unsaturated monomers are preferably selected, either alone or in combinations, from linear or branched, unsaturated carboxylic acids, that have been optionally partially or totally neutralized in the form of a It, where this or these unsaturated carboxylic acid(s) may be more particularly acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid. Suitable salts are in particular alkaline metal alkaline-earth metal and ammonium salts. It will be noted that, in the same way, in the final silicone graft polymer the anionic type organic group which comprises the radical (homo)polymerization result of at least one anionic monomer of the unsaturated carboxylic acid type may be, after reaction, post-neutralized with a base (soda, ammonia, and so on) to convert it into a salt.
According to the present invention, hydrophobic ethylenically unsaturated monomers are preferably selected, either alone or in combinations, from alkanol acrylic acid esters and/or alkanol methacrylic acid esters. Alkanols are preferably C1-C18 alkanols and more particularly C1-C12 alkanols. Preferred monomers are selected from the group consisting of isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate, tertio-butyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate or mixtures thereof.

A family of silicone polymers with a polysiloxane backbone graft with non silicone organic monomers that is particularly suitable for implementing the present invention comprises silicone polymers comprising in their structure a unit of following formula (XVII):
(Formula Removed)
wherein G1 radicals, being the same or different, represent hydrogen or a C1-C10 alkyl radical or a phenyl radical; G2 radicals, being the same or different, represent a C1-C10 alkyl group; G3 represents a polymer residue resulting from the (homo)polymerization of at least one ethylenically unsaturated anionic monomer; G4 represents a polymer residue resulting from the (homo)polymerization of at least one ethylenically unsaturated hydrophobic monomer; m and n are 0 or 1; a is an integer ranging from 0 to 50; b is an integer that may range from 10 to 350, c is an integer ranging from 0 to 50; provided one of these parameters a and c be different from 0.
Preferably, the unit of the hereabove formula (XVII) presents preferably at least one of, and even more preferably all, the following characteristics:
G1 radicals represent an alkyl radical, preferably a methyl radical;
n is different from zero, and G2 radicals represent a C1-C3 divalent radical, preferably a propylene radical;
G3 represents a polymer radical resulting from the (homo)polymerization of at least one monomer of the ethylenically unsaturated carboxylic acid type, preferably acrylic acid and/or methacrylic acid;
G4 represents a polymer radical resulting from the (homo)polymerization of at least one monomer of the (C1-C10) alkyl (meth)acrylate type, preferably isobutyl or methyl (meth)acrylate.
Examples of silicone graft polymers of following formula (XVII) are in particular polydimethyl siloxanes (PDMS) on which mixed polymer units of the poly(meth)acrylic acid type and methyl poly(meth)acrylate type have been graft, by means of a thiopropylene-type link.
Preferably, the number average molecular weight of the silicone polymers with a polysiloxane backbone graft with non silicone organic monomers of the invention does vary from about 10 000 to 1 000 000, and even more preferably from about 10 000 to 100 000.
Suitable silicone graft polymers to be used according to the present invention include the product marketed by 3M under the reference VS80.
H) anionic polyurethanes.
Polyurethanes to be preferably used according to the invention preferably have a base repeating unit of following formula (XVIII):
-X'-B"-X'-CO-NH-R-NH-CO-(XVIII)
wherein
X' represents O and/or NH,
B" is a divalent hydrocarbon radical, this radical being substituted or not, and
R is a divalent radical selected from the group consisting of alkylene radicals, branched or not, of the C6-C20 aromatic type, C1 to C20 aliphatic type, preferably C1-C6, C1 to C2 cycloaliphatic type, preferably C1-C6, these radicals being non substituted or substituted by one or more halogen, C1-C4 alkoxy, C6-C30 aryl, especially phenyl group(s).
Preferably, B" radical is a C1-C30 divalent radical, preferably C2-C10 and carries a group having one or more carboxylic function(s) and/or one or more sulfonic function(s), said carboxylic and/or sulfonic functions being in a free form or partially or totally neutralized by a mineral or an organic base, such as alkaline metal or alkaline-earth metal hydroxides, ammonia and alkyl amines or alkanol amines, organic amino acids. Preferably, B" is the divalent radical derived from dimethylol propionic acid.
R radical is advantageously selected from the group consisting of radicals of following formulas:
(Formula Removed)


wherein b is an integer ranging from 0 to 3, and c an integer ranging from 1 to 20, preferably ranging from 2 to 12.
In particular, R radical is selected from the group consisting of hexamethylene, 4,4'-biphenylene methane, 2,4- and/or 2,6-tolylene, 1,5-naphtylene, p-phenylene, methylene-4,4-bis-cyclohexyl radicals and isophorone divalent radical derivative.
Fixing polyurethanes to be used may comprise silicone grafts and hydrocarbon silicone grafts.
A polyurethane to be used may advantageously comprise in addition at least one polysiloxane sequence and its base repeating unit has for example following general formula (XIX):
-X'-P-X'-CO-NH-R-NH-CO- (XIX)
wherein:
P is a polysiloxane segment,
X' represents 0 and/or NH, and
R is a divalent radical selected from the group consisting of branched or not, alkylene radicals of the C6-C20 aromatic type, C1-C20 aliphatic type, preferably C1-C6, C1-C20 cycloaliphatic type, preferably C1-C6, these

radicals being non substituted or substituted by one or more halogen, C1-C4 alkoxy, C1-C30 aryl, especially phenyl group(s).

R radical is advantageously selected from the group consisting of radicals of following formulas:
(Formula Removed)
wherein b is an integer ranging from 0 to 3, and c an integer ranging from 1 to 20, preferably ranging from 2 to 12.
In particular, R radical is selected from the group consisting of hexamethylene, 4,4'-biphenylene methane, 2,4- and/or 2,6-tolylene, 1,5-naphtylene, p-phenylene, methylene-4,4-bis-cyclohexyl radicals and isophorone derived divalent radical.
Advantageously, P polysiloxane segment has following general formula (XX):
(Formula Removed)
wherein:
A" groups, which may be the same or different, are selected from the group consisting of, on the one hand, monovalent C1 to C20 hydrocarbon
groups, substantially free from any ethylenic unsaturation and, on the other hand, aromatic groups,
Y represents a divalent hydrocarbon group, and
Z represents an integer, selected so that the average molecular weight of the polysiloxane segment be from 300 to 10 000.
Generally, Y divalent group is selected from alkylene groups of formula -(CH2)a-, wherein a represents an integer that may range from 1 to 10.
A" groups may be selected from C1-C18 alkyl groups, especially from methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl groups; cycloalkyl groups, especially cyclohexyl group; aryl groups, in particular phenyl and naphthyl; arylalkyl groups, in particular benzyl and phenylethyl, as well as tolyl and xylyl groups.
Suitable examples of fixing polyurethanes encompass in particular copolymer of dimethylol propionic acid / isophorone diisocyanate /neopentyl glycol/ polyester diols (also known under the trade name polyurethane-1, INCI name) marketed under the trade name Luviset® PUR by BASF, copolymer of dimethylol propionic acid, isophorone diisocyanate, neopentyl glycol, polyester diols, silicone diamine (also known under the trade name polyurethane-6, INCI name) marketed under the trade name Luviset® if PUR A by BASF.
AVALURE UR 450 is another suitable anionic polyurethane to be used.
Sulfoisophthalate group containing polymers may also be used, such as AQ55 and AQ48 polymers marketed by EASTMAN.
According to the invention, anionic polymers are preferably selected from the group consisting of acrylic acid copolymers, such as terpolymer of acrylic acid/ ethyl acrylate/ N-tertiobutyl acrylamide marketed under the name ULTRAHOLD STRONG® by BASF, copolymers of methacrylic acid and ethyl acrylate, in particular in aqueous dispersion, such as LUVIFLEX SOFT and LUVIMER MAE marketed by BASF. Copolymers derived from crotonic acid, such as terpolymers of vinyl acetate/ vinyl tertio-butyl benzoate/ crotonic acid and terpolymers of crotonic acid/ vinyl acetate/ vinyl neododecanoate

marketed under the name Resin 28-29-30 by NATIONAL STARCH, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and esters thereof, such as a copolymer of methyl vinylether and monoesterified maleic anhydride marketed under the name GANTREZ® ES 425 by ISP, LUVISET SI PUR, MEXOMERE PW, elastomer or non elastomer, anionic polyurethanes, sulfoisophthalate group-containing polymers, anionic graft silicone polymers, as well as AMERHOLD DR 25 and VS 80.
Amphoteric polymers to be used according to the invention may be selected from the group consisting of polymers comprising B'" and C'" units statistically distributed within the polymer chain, wherein B'" represents a unit derived from a monomer comprising at least one basic nitrogen atom and C'" represents a unit derived from an acid monomer comprising one or more carboxylic or sulfonic groups, or B'" and C'" may represent groups derived from carboxybetaine or sulfobetaine zwitterionic monomers; B'" and C'" may also represent a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, wherein at least one amine group carries a carboxylic or sulfonic group bound by means of a hydrocarbon group, or B'" and C'" are part of a chain of an ethylene dicarboxylic unit-containing polymer, one carboxylic group of which was reacted with a polyamine comprising one or more primary or secondary amine group(s).
Amphoteric polymers corresponding to the hereabove given definition that are more particularly preferred are selected from the group consisting of following polymers:
(1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group, such as more particularly acrylic acid, methacrylic acid, maleic acid, alphachloracrylic acid, and from a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as more particularly dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkyl methacrylamide and acrylamide. Such compounds are described in the American patent n° 3,836,537.

The vinyl compound may also be a dialkyldiallyl ammonium salt, such as diethyl diallylammonium chloride.
(2) polymers comprising units derived:
a) from at least one monomer selected from the group consisting of
acrylamides or methacrylamides substituted on the nitrogen atom with an
alkyl group,
b) from at least one Acidic comonomer containing one or more reactive
carboxylic group(s), and
from at least one basic monomer, such as esters with primary, secondary, tertiary and quaternary amine substituents of the acrylic and methacrylic acids, and the quaternization product of the dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are groups which alkyl groups do comprise from 2 to 12 carbon atoms and more particularly N-ethyl acrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octyl acrylamide, N-decyl acrylamide, N-dodecyl acrylamide as well as corresponding methacrylamides.
Acidic comonomers are selected more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having from 1 to 4 carbon atoms of the maleic or fumaric acids or anhydrides. Preferred basic comonomers are aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl, N-tertio-butylaminoethyl methacrylates. Particularly used are copolymers which CTFA name (4th Ed, 1991) is octyl acrylamide/ acrylate/ butylaminoethyl methacrylate copolymer, such as products marketed under the name AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH.
(3) crosslinked and partially or totally alkylated polyaminoamides
derived from polyaminoamides of general formula:
(Formula Removed)
wherein R4 represents a divalent group derived from a saturated dicarboxylic acid, from an aliphatic, ethylene double bond-mono or dicarboxylic acid, from an ester of a lower alkanol having from 1 to 6 carbon atoms of these acids or from a group resulting from the addition of any of said acids with a bis-primary or bis-secondary derivative amine, and Z represents a group of a bis-primary, mono or bis-secondary polyalkylene polyamine and represents preferably:
a) in amounts ranging from 60 to 100% by mole, the group
wherein x=2 and p=2 or 3, or x=3 and p=2
this group being derived from diethylene triamine, triethylene tetraamine or dipropylene triamine;
b) in amounts ranging from 0 to 40% by mole, the hereabove (XXII) group, wherein x=2 and p=1 and which is derived from ethylene diamine, or the group derived from piperazine
(Formula Removed)
c) in amounts ranging from 0 to 20% by mole, the -NH-(CH2)6-NH-group derived from hexamethylene diamine, these polyaminoamines being crosslinked by adding a bifunctional crosslinking agent selected from the group consisting of epihalohydrines, diepoxides, dianhydrides, bis-unsaturated derivatives, using from 0.025 to 0.35 mole of crosslinking agent

per amine group of the polyaminoamide, and alkylated by reaction with acrylic acid, chloracetic acid or an alkane-sultone or salts thereof.
Saturated carboxylic acids are preferably selected from acids having from 6 to 10 carbon atoms, such as adipic, 2,2,4-trimethyl adipic and 2,4,4-trimethyl adipic, terephthalic acids, ethylene double bond-acids as, for example, acrylic, methacrylic, itaconic acids. Alkane-sultones used in the alkylation are preferably propane- or butane-sultone, alkylating agent salts are preferably sodium or potassium salts.
(4) polymers comprising zwitterionic units of formula:

(Formula Removed)
wherein R5 represents an unsaturated polymerizable group, such as an acrylate, a methacrylate, acrylamide or methacrylamide group, y and z each represent an integer from 1 to 3, R6 and R7 represent a hydrogen atom, a methyl, ethyl or propyl group, R8 and R9 represent a hydrogen atom or an alkyl group, so that the sum of the carbon atoms in R10 and R11 does not exceed 10.
Polymers comprising such units may also comprise units derived from non zwitterionic monomers, such as dimethyl- or diethylaminoethyl acrylate or methacrylate, or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.
(5) polymers derived from chitosan comprising monomer units of following formulas:

(Formula Removed)
(XXIV) unit being present in amounts ranging from 0 to 30%, (XXV) unit in amounts ranging from 5 to 50% and (XXVI) unit in amounts ranging from 30 to 90%, being admitted that in this F unit, R10 represents a group of formula:

(Formula Removed)
wherein if q=0, R11, R12 and R13, being the same or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkyi amine or a dialkyi amine residue, optionally interrupted with one or more nitrogen atom(s) and/or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic group(s), an alkylthio residue which alkyl group carries an amino residue, where at least one of the R17, R18 and R19 groups are in that case a hydrogen atom;
or if q=1, R11, R12 and R13 each represent a hydrogen atom, as well as salts formed by these compounds with bases or acids.
(6) Polymers derived from chitosan N-carboxyalkylation.
(7) Polymers with units of following general formula (XXVIII) described
for example, in the French patent 1 400 366:
(Formula Removed)
wherein R14 represents a hydrogen atom, a CH3O, CH3CH2O, or a phenyl group, R15 represents hydrogen or a lower alkyl group, such as methyl, ethyl, R16 represents hydrogen or a lower alkyl group, such as methyl, ethyl, R17 represents a lower alkyl group, such as methyl, ethyl or a group of following formula: -R18-N(R16)2, R18 representing a -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH(CH3)- group, R16 being as previously defined,
as well as higher homologues of these groups and containing up to 6 carbon atoms.
(8) Amphoteric polymers of the -D-X-D-X- type selected from:
a) polymers obtained by reacting chloracetic acid or sodium chloracetate on compounds comprising at least one unit of formula: -D-X"-D-X"-D- (XXIX)
where D represents a group
(Formula Removed)
and X" represents symbol E or E1, where E or E', being the same or different, represent a bivalent group, which is a straight or branched chain alkylene group comprising up to 7 carbon atoms in the main chain non substituted or substituted with hydroxyl groups, that may moreover comprise oxygen, nitrogen, sulfur atoms, from 1 to 3 aromatic and/or heterocyclic rings; oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkyl amine, alkenyl amine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.
b) Polymers of formula: -D-X"-D-X"- (XXX)
where D represents a group
(Formula Removed)
and X" represents symbol E or E' and at least one time E1; E being as previously defined and E1 is a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl groups and comprising one or more nitrogen atom(s), said nitrogen atom being substituted with an alkyl chain optionally interrupted by an oxygen atom and necessarily comprising one or more carboxyl function(s) or one or more hydroxyl function(s) that were betainized by reacting with chloracetic acid or sodium chloracetate.
(9) Copolymers of alkyl(C1-C5)vinylether and maleic anhydride partially modified by half-amidification with a N,N-dialkylaminoalkyl amine, such as N,N-dimethylaminopropyl amine or by half-esterification with a N,N-dialkanol amine. These copolymers may also comprise other vinyl comonomers, such as vinyl caprolactame.

According to a preferred embodiment of the invention, fixing amphoteric polymers to be used in the method of the invention may be selected from the group consisting of branched, block copolymers comprising:
(a) non ionic units derived from at least one monomer selected from the
group consisting of C1-C20 alkyl (meth)acrylates, N-mono-(C2-C12 alkyl)-
(meth)acrylamides and N,N-di-(C2-C12 alkyl)-(meth)acrylamide,
(b) anionic units derived from at least one monomer selected from
acrylic acid and methacrylic acid, and
(c) polyfunctional units derived from at least one monomer comprising
at least two unsaturated polymerizable functional groups,
and having preferably a structure formed from hydrophobic blocks onto which several more hydrophilic blocks are fixed through polyfunctional units
(c).
Preferably, amphoteric polymers present at least two glass transition temperatures (Tg), one of which at least being higher than 20 °C and the other being lower than 20°C.
Preferred amphoteric polymers are polymers comprising units derived:
a) from at least one monomer selected from the group consisting of
acrylamides or methacrylamides substituted on the nitrogen atom by an alkyl
group,
b) from at least one Acidic comonomer containing one or more reactive
carboxylic group(s), and
c) from at least one basic comonomer, such as primary, secondary,
tertiary and quaternary amine substituent esters of acrylic and methacrylic
acids, and the quaternization product of dimethylaminoethyl methacrylate
with dimethyl or diethyl sulfate.
Suitable examples include especially polymers marketed under the name AMPHOMER by NATIONAL STARCH.
The composition medium containing the fixing polymer is an aqueous, alcoholic or hydroalcoholic cosmetically acceptable medium. Cosmetically acceptable organic solvents are preferably monoalcohols, polyols or ethers of

these alcohols or polyols. Ethanol, isopropanol, glycerol, propylene glycol, propylene glycol monomethyl ether may be mentioned for example. Ethanol is a particularly preferred solvent.
Typically, the fixing polymer(s) represent(s) from 0.1 to 20%, preferably from 1 to 15% by weight of the composition total weight. Applying the fixing polymer-containing composition may occur for example with a spray, that is to say an aerosol device or a pump container dispensing a foam or fine droplets of a solution.
According to a particular embodiment of the invention, the step for applying the reducing composition and/or the fixing step do(es) occur under heating or is (are) immediately followed with heating.
Typically, the method of the invention comprises, following the step for applying the reducing composition, and/or following the oxidation fixing step, a step consisting in rinsing the keratin fibers with water.
The reducing composition may also be applied as the hair winding up is being effected. Typically, the reducing composition is then allowed to react for a time period ranging from 1 to 50 minutes, preferably from 1 to 30 minutes.
It is also possible after having applied the reducing composition, to submit the hair to a thermal treatment by heating to a temperature ranging from 30 to 250°C for part of or all the reaction time. In praxis, this operation may be conducted by means of a hood hair dryer, a hair dryer, a round iron or a flat iron, an IR-emitting device and other heating devices, and in some cases under a plastic film.
A rinsing operation of the keratin fibers is then optionally effected with water, and then a drying operation.
The drying step may be complete or partial, it may be done for example by means of a domestic hair dryer or a hood hair dryer or a heating hair cap, or be effected by carefully wringing the hair out. A heating system will be preferably used. The drying is preferably complete.

The oxidizing composition enabling to reform the keratin disulfide bonds is then applied onto the dried or wringed hair, generally for a reaction time ranging from 2 to 30 minutes. The hair is then rinsed off thoroughly, preferably with water, then the optionally present tensioning materials are removed.
As previously explained, the method of the invention may comprise a step for applying a hair-care composition containing a cationic polymer and/or a silicone, preferably an amine silicone. As an example, the hair-care composition may be applied at following steps of the method object of the invention:
- prior to setting the hair under tension,
- between the hair tensioning step and the reducing composition
applying step,
- after the rinsing step with water following the reducing composition
applying step and before the oxidation fixing step, and/or
- after the rinsing step with water following the oxidation fixing step.
Preferably, the hair-care composition is applied before the step for
mechanically setting the keratin fibers under tension.
Preferably, the hair-care composition applying step is followed with a rinsing, preferably a rinsing with water.
After having rinsed off the reducing agent, the hair is dried in form or wringed out, then fixed with the fixing agent.
The permanently reshaping method according to the invention, in particular thanks to the provision of a simple intermediary drying step between the reducing step and the oxidizing step, makes it possible to durably add some texture, weight and body to the hair, to provide stylability, and special hair root-volume, and especially to short-length and thin hair, for several weeks.
The hair colour does barely change immediately after the treatment.
In addition, a protecting effect on artificially coloured hair is observed upon repeated washing with shampoos. In other words, the method for

permanently reshaping the keratin fibers of the invention does scarcely deteriorate or does not deteriorate at all the artificial hair colour.
Lastly, the provision in the method of the invention of a step consisting in applying a reducing composition and an oxidizing composition makes it possible to durably reshape the keratin fibers in a way similar to that observed with the usual permanent reshaping methods.
It is another object of the invention to provide a kit comprising:
- at least one first compartment comprising a reducing composition,
such as described hereabove, and
- at least one second compartment comprising an oxidizing
composition, such as described hereabove.
Preferably, this kit also comprises means for mechanically setting the hair under tension, and especially tulip-type curlers.
The invention will be illustrated using the following, non limitative examples.
Example 1
A reducing composition and an oxidizing composition were prepared to implement a method for permanently reshaping the hair according to the invention.
Formulations are as follows:
Composition example
In the following composition examples, percentages are expressed by weight as related to the composition total weight.
Reducing composition (1):
Cysteine 2%
Ammonium thioglycolate in

71% aqueous solution 0.7%
Monoethanol amine 1.4%
Ammonium bicarbonate 1.3%
Sodium cocoamphopropionate 0.7%
Mexomer PO (60% active material) 0.8%
Demineralized water qs 100%
pH value 8.8 Oxidizing composition (2)
50% Hydrogen peroxide 2.4%
Stabilizers 0.01%
Citric acid 0.05%
Merquat 100 (Polyquaternium 6) 0.6%
Lauramine oxide 1.1%
Demineralized water qs 100%
pH value 3
Spray composition (3)
LUVISET Si PUR A 5.13%
AQ48 6.15%
Alcohol 28.95%
Water qs 100%
Aerosol containing 65 g of composition (3) and 35 g of dimethyl ether propellant.

Hair-care composition 4
Wacker Belsil ADM LOG 1 10%
Water qs 100%
Example 2 methods for permanently reshaping the hair according to the invention
Procedure with spray 3
The hair was shampooed and wringed out.
The hair was wound around the tulip-type curlers.
Aerosol composition (3) was generously spread onto the whole hair.
The reducing composition (1) was then applied onto the hair. The
composition was allowed to react for 15 minutes, then the hair was rinsed off.
The hair was then dried under a heating hood hair dryer.
The oxidizing composition (2) was then applied.
After 5 minutes, the hair was rinsed and the tulip-type curlers removed.
A lifting could be observed on the roots and the hair appeared more dense.
After several shampoos, these advantages did still persist.
Procedure with hair-care composition 4
The hair was shampooed and wringed out.
The hair-care composition (4) was applied.
The hair was wound around the tulip-type curlers.
The reducing composition (1) was then applied onto the hair. The
composition was allowed to react for 15 minutes, then the hair was rinsed off.
The hair was then dried with a hair dryer.
The oxidizing composition (2) was then applied.
After 5 minutes, the hair was rinsed and the tulip-type curlers removed.
A lifting could be observed on the roots and the hair appeared more dense.
After several shampoos, these advantages did still persist.

CLAIMS
1. A method for permanently reshaping the keratin fibers, especially hair
keratin fibers, comprising:
- a step for setting the keratin fibers under tension, then
- a step for applying a reducing composition onto the keratin fibers so
as to reduce the keratin disulfide bonds, said reducing composition
comprising in a cosmetically acceptable medium, from 0.1 to 3% by
weight of at least one reducing agent, as related to the reducing
composition total weight, then, after an optional rinsing operation,
- a step for drying the keratin fibers, then
- an oxidation fixing step, so as to reform said bonds, by applying an
oxidizing composition onto the keratin fibers.

2. A method according to claim 1, characterized in that the keratin fiber
drying is a partial drying or a complete drying.
3. A method according to claim 1, characterized in that the keratin fiber
drying is a complete drying.
4. A method according to any preceding claim, characterized in that the
keratin fiber tensioning step is carried out by means of tulip-type curlers.
5. A method according to any preceding claim, characterized in that the
reducing agent(s) is or are selected from the group consisting of sulfites,
bisulfites, thiols and phosphines.
6. A method according to any of claims 1 to 4, characterized in that the
reducing agent(s) is or are selected from the group consisting of L-cysteine,
D-cysteine, L,D-cysteine, and their salts, thiolactic acid, salts and esters
thereof, thioglycolic acid, salts and esters thereof, and mixtures thereof.
7. A method according to any preceding claim, characterized in that the
reducing agent(s) represent(s) from 0.3 to 3% by weight, as related to the
reducing composition total weight.

8. A method according to any preceding claim, characterized in that the
reducing composition is allowed to react for 2 to 50 minutes, preferably for 2
to 30 minutes, and even more preferably for 5 to 20 minutes.
9. A method according to any preceding claim, characterized in that the
pH value of the reducing composition does vary from 7.5 to 11, preferably
from 8 to 9.5.

10. A method according to any preceding claim, characterized in that
the oxidizing composition comprises at least one oxidizing agent selected
from hydrogen peroxide, carbamide peroxide, alkaline bromates,
polythionates, persalts, such as perborates, percarbonates and persulfates.
11. A method according to claim 10, characterized in that the oxidizing
agent(s) generally represent(s) from 0.1 to 10%, preferably from 0.5 to 5% by
weight as related to the oxidizing composition total weight.
12. A method according to any preceding claim, characterized in that
the oxidizing composition is allowed to react for 2 to 30 minutes, preferably
for 2 to 15 minutes, more preferably for 2 to 7 minutes.
13. A method according to any preceding claim, characterized in that
the pH value of the oxidizing composition does vary from 1.5 to 4.5,
preferably from 2 to 3.5.
14. A method according to any preceding claim, characterized in that it
comprises, following the reducing composition applying step and/or following
the oxidation fixing step, a step consisting in rinsing the keratin fibers with
water.
15. A method according to any preceding claim, characterized in that
the reducing composition applying step is effected under heating or is
immediately followed with a heating operation.
16. A method according to any preceding claim, characterized in that
the reducing composition and the oxidizing composition present
independently from each other in the form of a lotion, a gel, thickened or not,
a foam, or a cream.

17. A method for permanently reshaping the hair according to any
preceding claim, characterized in that the step for mechanically setting the
keratin fibers under tension does occur after a hair-care composition applying
step which contains a cationic polymer and/or a silicone, preferably, an amino silicone.
18. A method for permanently reshaping the hair according to claim 17,
characterized in that the hair-care composition applying step is followed with
a rinsing operation.
19. A method for permanently reshaping the hair according to any
preceding claim, characterized in that it comprises a step for applying a fixing
polymer-containing composition.
20. A method for permanently reshaping the hair according to claim 16,
characterized in that the fixing polymer-containing composition is applied
between the step for setting the keratin fibers under mechanical tension and
the step for applying the reducing composition.
21. A kit comprising:
- at least one first compartment comprising a reducing composition,
such as defined in claim 1, and
- at least one second compartment comprising an oxidizing
composition, such as defined in claim 1.
22. A kit according to claim 21, comprising in addition means for setting the hair under mechanical tension.