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 reducing composition and a step for applying an oxidizing composition, this method being associated with the use of a means for mechanically setting the hair under tension, said means being flexible and closable upon itself, so as to form a curl.
The most usual art to obtain a permanent 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. This method thus makes it possible to wave the hair (perm method). The new shape that has been 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 using a set.
Tensioning effected by curlers enables to provide a hair lifting at the root level leading to an expansion of the hair volume, thus inherently causing a curling of the whole hair strand.
However, many women would like to increase their hair volume, without wishing to get frizzy hair. In other words, while it would be desirable to be able to produce a hair volume expansion, there is also a need for replacing the curliness along the whole hair strand inherent in the hair shaping traditional methods which is substantially bidimensional, with full three-dimensional spiral-shaped curls.
There is hence a need for a method for permanently reshaping the hair that would be able to durably provide a hair volume expansion by lifting the same at the root level, together with three-dimensional formed curls.
While the hair setting using a round iron makes it possible to obtain this type of spiral-shaped full curls, these do disappear as soon as the first shampoo is done, because of the breaking of the created ionic and saline bonds.
Using usual rollers during the traditional hair shaping method is not satisfying either since this method type does lead to a temporally poor quality hair fixing and does not allow three-dimensional shaped curls to be formed.
No one of the described methods does thus lead to a fully satisfying permanently reshaping method as regards the hereabove mentioned problems.
The applicant discovered that the previously mentioned drawbacks of the prior art are solved thanks to a method for permanently reshaping the keratin fibers comprising in particular a keratin fiber drying step between a reducing composition applying step and the oxidation fixing step, such method being associated with the use of means for mechanically setting the the keratin fibers under tension, said means being flexible and closable upon themselves so as to form a curl. It is thus an object of the invention to provide a method for permanently reshaping the keratin fibers, especially for permanently reshaping the hair, comprising:
- a step for mechanically setting the keratin fibers under tension by
winding the same around a mechanical tensioning means, said means being
flexible and closable upon itself, so as to form a curl, then
- a step for applying onto the keratin fibers a reducing composition, so
as to reduce the keratin disulfide bonds, then after an optional rinsing
operation,
- a step for drying the keratin fibers, then
- an oxidation fixing step, to reform said bonds, by applying onto the
keratin fibers an oxidizing composition.
The hereabove mentioned method enables to produce rapidly and durably a keratin fiber volume expansion, and especially a hair volume
expansion by lifting the same at the root level, together with three-dimensional formed curls.
As used herein, "flexible" is intended to mean a device comprising for all or part of its whole lenght a material that is sufficiently supple for said device be able to be folded upon itself and form a curl. Such material may be a plastic malleable, molded, aerated or foamed material, a metallized or non metallized paper, a fibrous material, such as cord and twine, or a non woven material.
As used herein, "closable" is intended to mean a device which makes it possible to form a curl along at least one part of its lenght.
Preferably, the mechanical tensioning means is a curler or a suitable curlpaper. Most preferably, the curler used during the hair tensioning step is a tulip-type curler consisting in a body-forming extended rod, ending at one end thereof with a head provided with at least one hole. The curler body is made in a 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 FR2 602 650.
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. Using one or more tulip-type curler(s) in the context of the method of the invention also enables to avoid the problematic marks formed at the hair root and to obtain three-dimensional, spiral-shaped curls, which amplitude does vary depending on the amount of tulip-type curlers used, rather than the bidimensional waving of the hair strands which is produced with cylindrical curlers. The winding of the curlers may be conducted either on the whole hair length, or on half-length for long-length hair.
Depending on the hair shape and on the expected curl volume, the winding up is carried out on more or less thick hair strands.
To obtain a result similar to that described hereabove, one or more curlpapers may also be used instead of tulip-type curlers, provided that the hair be wound on the curlpaper and this one be folded upon itself to form a curl.
The reducing composition used in the method of the invention does typically comprise, in a cosmetically acceptable medium, at least one reducing agent selected from 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, and mixtures thereof.
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, p-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.
Even more preferably, cysteine is used.
The reducing agent(s) each preferably represent(s) from 0.5 to 10%, preferably from 1 to 8%, more preferably from 2 to 7% 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.
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 practice, 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 at least one 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 CH3
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, R5, R6, 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 (C-|-C4)alkyl groups, acrylic or
methacrylic acids or esters thereof, vinyl lactames, such as vinyl pyrrolidone or vinyl caprolactame, and vinyl ester 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 QUATPIOObyCIBAGEIGY,
- 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; Rg represents a hydrogen atom or a methyl radical; Ry and RQ, 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(C<|-C4)alkyl group, or Ry and RQ may
represent together with the nitrogen atom to which they are bound, heterocyclic groups, such as piperidinyl or morpholinyl; Ry and RQ
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, tart rate, 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 quaternary diammonium polymer containing repeating units of following formula (VII):
(Formula Removed)
. RH. Rl2 anc' 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 RIQ. RH- Rl2 anc' 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 RIQ. RH, Rl2 ancl R13 represent a linear or branched, C-|-CQ alkyl radical, substituted with a nitrite, ester, acyl, amide or -CO-O- Ri4-D or -CO-NH- R-J4-D group, where R^4 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, RIO and R-|2 may form 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: -O-Z-O-, where Z represents a
linear or branched hydrocarbon radical or a group having one of the following
formulas:
(Formula Removed)
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) an 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 RIQ, R11. R12 anc' 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 PO may be especially mentioned;
(11) Quaternary polyammonium compounds comprising repeating units of formula (IX):
(Formula Removed)
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(Ci-
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) Academie 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):

(Structure Removed)
avec -> with
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-1,1'(hexa-2,2,2',2',3,3'-trimethylsiryloxy) 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 (Ct-Cao) 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: R2SJO2/2, RaSiOi/2, RSiO3/2 and SiO4/2,
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 C6-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 (Ci2)alkyl
methicone copolyol marketed by DOW CORNING under the trade name Q2
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 d-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.
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 7 minutes.
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 alky) 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.
As previously explained, the method of the invention comprises a step for applying a reducing composition onto the keratin fibers, especially onto the hair, then a step for applying an oxidizing composition.
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 practice, 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 is preferably complete, and 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.
The oxidizing composition enabling to reform the keratin disulfide bonds is then applied on dry hair, generally for a reaction time ranging from 2 to 30 minutes. The hair is then rinsed off thoroughly, preferably with water, then the present tensioning means 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 optional rinsing step with water following the reducing
composition applying step and before the 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. Thus, according to the present invention, the step for mechanically setting the keratin fibers under tension is preferably carried out after a step for applying a hair-care composition containing a cationic polymer and/or a silicone, preferably an amino silicone.
The hair-care composition applying step is preferably followed with a rinsing, preferably a rinsing with water.
It is another object of the invention to provide a kit combining at least:
- tensioning means, as previously described,
- a first compartment comprising a cosmetic composition containing at
least one reducing agent, and
- a second compartment comprising a cosmetic composition,
containing at least one oxidizing agent.
The invention will be illustrated with the following 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 4%
Ammonium thioglycolate in
71% aqueous solution 1.5%
Monoethanolamine 2.8%
Ammonium bicarbonate 2.7%
Sodium cocoamphopropionate 1.4%
Mexomer PO (60% active material) 1.6%
Demineralized water qs 100%
pH value 8.8
Oxidizing composition (2)
Hydrogen peroxide 4.8%
Stabilizers 0.03%
Citric acid 0.1%
Merquat 100 (Polyquatermium 6) 1.25%
Lauramine oxide 2.15%
Demineralized water qs 100%
pH value 3
Comparative assays conducted on heads with any type of hair, i.e. Asian, Indian and Caucasian, natural or sensitized hair, were performed by applying the hereabove described compositions, in the context of a hair reshaping method in accordance with the invention, as described in example 2. With the method of the invention, better results were obtained as
regards the curl quality as compared to a traditional procedure. Three-dimensional curls were obtained, as well as a very natural hair feel.
Moreover, a protecting effect on artificially coloured hair is observed both during the implementation of this method, 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.
Example 2 method for permanently reshaping the hair
The hair of a model was shampooed, then rinsed off.
The whole hair was wound around tulip-type curlers.
The reducing composition 1 was applied, a plastic film was wrapped around
head. The reaction was allowed to proceed under a heating hood hair dryer
for 15 minutes.
The plastic film was removed, then the hair was rinsed while the tulip-type
curlers still remained in place.
The hair was then placed under heating hood hair dryer until it is completely
dry.
Oxidizing composition 2 was then applied and was left to stand for 5 minutes.
Tulip-type curlers were then removed and the hair rinsed off.

CLAIMS
1. A method for permanently reshaping the keratin fibers, more
particularly for permanently reshaping the hair, comprising:
- a step for mechanically setting the keratin fibers under tension by
winding the same around a mechanical tensioning means, said means being
flexible and closable upon itself, so as to form a curl, then
- a step for applying onto the keratin fibers a reducing composition, so
as to reduce the keratin disulfide bonds, then after an optional rinsing
operation,
- a step for drying the keratin fibers, then
- an oxidation fixing step, to reform said bonds, by applying onto the
keratin fibers an oxidizing composition.

2. A method according to claim 1, characterized in that the mechanical
tensioning means is a curler or a curlpaper.
3. A method according to claim 2, characterized in that the curler is a
tulip-type curler.
4. A method according to any preceding claim, characterized in that the
reducing composition comprises, in a cosmetically acceptable medium, at
least one reducing agent selected from sulfites, bisulfites, thiols and
phosphines.
5. A method according to claim 4, characterized in that the reducing
agent 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.
6. A method according to claim 4 or 5, characterized in that the reducing agent represents from 0.5 to 10%, preferably from 1 to 8%, more preferably from 2 to 7% by weight, as related to the reducing composition total weight.
7. A method according to any preceding claim characterized in that the reducing composition is left to stand for 1 to 50 minutes, preferably for 1 to 30 minutes.
8. 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.
9. 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.

10. A method according to claim 9, 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.
11. A method according to any preceding claim, characterized in that
the oxidizing composition is left to stand for 2 to 30 minutes, preferably for 2
to 15 minutes, more preferably for 2 to 7 minutes.
12. 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.
13. 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.
14. 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.
15. 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, thickened or not, a
cream, a gel or a foam.
16. Permanent reshaping method according to any preceding claim,
characterized in that the step for mechanically setting the keratin fibers under
tension does occur after a step for applying a hair-care composition which
contains a cationic polymer and/or a silicone, preferably, an amino silicone.
17. Permanent reshaping method according to claim 16, characterized
in that the hair-care composition applying step is followed with a rinsing
operation.
18. A kit combining at least:

- mechanical tensioning means, as defined in claim 1,
- a first compartment comprising a cosmetic composition containing at
least one reducing agent, and

- a second compartment comprising a cosmetic composition,
containing at least one oxidizing agent.