US20080185014A1

US20080185014A1 - Method for permanently reshaping keratin fibers comprising applying a poorly concentrated reducing composition and intermediate drying

Info

Publication number: US20080185014A1
Application number: US12/003,320
Authority: US
Inventors: Catherine Campain
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2006-12-22
Filing date: 2007-12-21
Publication date: 2008-08-07
Also published as: ATE456932T1; EP1935275A1; EP1935275B1; ES2341584T3; FR2910247A1; JP2008208115A; DE602007004662D1; CN101244017B; CN101244017A; BRPI0705746A; KR20080059109A; MX2007016470A; FR2910247B1

Abstract

The present disclosure relates to a method for permanently reshaping the keratin fibers, for example for permanently reshaping the hair, comprising:

- mechanically setting the keratin fibers under tension by winding the same around at least one mechanical tensioning device, said at least one device being flexible and closable upon itself, so as to form a curl,
- applying onto the keratin fibers at least one reducing composition, so as to reduce the keratin disulfide bonds,
- an optional rinsing,
- drying the keratin fibers, and
- applying at least one oxidizin composition, to reform said bonds.

Description

This application claims benefit of U.S. Provisional Application No. 60/907,307, filed Mar. 28, 2007, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. § 119 to French Patent Application No. FR 0655915, filed Dec. 22, 2006, the contents of which are also incorporated herein by reference.
Disclosed herein is a method for permanently reshaping hair comprising a hair drying step between applying at least one reducing composition to the hair and applying at least one oxidizing composition to the hair, this method being associated with the use of a device for mechanically setting the hair under tension, said device being flexible and closable upon itself, so as to form a curl.
The most usual art to obtain a permanent deformation of the hair comprises, in a first step, 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, 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, may be temporally substantially long-lasting and may resist washing operations with water or shampoo, as opposed to the usual simple methods for temporarily reshaping the hair using a set.
Tension provided by curlers often allows one 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, some people may like to increase their hair volume, without obtaining frizzy hair. In other words, while it may 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 are often 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 often 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 may 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 inventors have found, surprisingly, that the previously mentioned drawbacks of the prior art may be solved thanks to a method for permanently reshaping the keratin fibers, comprising drying the keratin fibers between applying at least one reducing composition and applying at least one oxidation fixing composition, such method being associated with the use of devices for mechanically setting the keratin fibers under tension, said devices being flexible and closable upon themselves so as to form a curl. Thus, disclosed herein is a method for permanently reshaping the keratin fibers, such as for permanently reshaping the hair, comprising:
mechanically setting the keratin fibers under tension by winding the same around a mechanical tensioning device, said device being flexible and closable upon itself, so as to form a curl;
applying onto the keratin fibers at least one reducing composition, so as to reduce the keratin disulfide bonds; optionally rinsing the keratin fibers,
drying the keratin fibers; and
applying onto the keratin fibers at least one oxidizing composition.
The hereabove mentioned method can allow one to produce, rapidly and durably, a keratin fiber volume expansion, such as a hair volume expansion, by lifting the keratin fibers at the root level, together with three-dimensional formed curls.
As used herein, “flexible” means a device comprising for all or part of its whole length a material that is sufficiently supple for said device be able to be folded upon itself and form a curl. Such material may, for example, 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” means a device which makes it possible to form a curl along at least one part of its length.
In at least one embodiment, the mechanical tensioning device is a curler or a suitable curlpaper. In another embodiment, the curler used during hair tensioning is a tulip-type curler comprising a body-forming extended rod, ending at one end thereof with a head comprising at least one hole. The curler body is made in a flexible material, so that its free end may be introduced into the at least one head hole and be fixedly maintained there by an elastic clamping. A curler of the hereabove type, suitable for implementing the method of the disclosure is, for example, described in the French Patent Application No. FR 2 602 650.
Using at least one tulip-type curler can make 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 often happens with most cylindrical curlers. Using at least one tulip-type curler in the context of the method disclosed herein also may allow one to avoid the problematic marks often formed at the hair root and to obtain three-dimensional, spiral-shaped curls, the amplitude of which may vary depending on the amount of tulip-type curlers used, rather than the bidimensional waving of the hair strands which is often produced with cylindrical curlers. The winding of the at least one curler 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, at least one curlpaper may be used instead of the at least one tulip-type curler, provided that the hair be wound on the at least one curlpaper and this curlpaper is folded upon itself to form a curl.
The at least one reducing composition used in the method disclosed herein can comprise, in a cosmetically acceptable medium, at least one reducing agent chosen from sulfites, bisulfites, thiols and phosphines.
Suitable examples of sulfites and bisulfites to be used include, but are not limited to, alkaline metal or alkaline-earth metal, or ammonium sulfites or bisulfites, and sodium, potassium or monoethanol amine sulfite or bisulfite.
In at least one embodiment, the at least one thiol used as the at least one reducing agent in the reducing composition is chosen from cysteine and derivatives thereof, such as N-acetylcysteine, cysteamine and derivatives thereof, such as from 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 at least one reducing composition used according to the disclosure further include, but are not limited to, sugar N-mercapto alkyl amides, such as N-(mercapto-2-ethyl)gluconamide, β-mercaptopropionic acid and derivatives thereof; thiomalic acid; pantheteine; N-(mercaptoalkyl)ω-hydroxyalkyl amides, such as those described in the European Patent Application Publication No. EP-A-354 835 and N-mono- or N,N-dialkylmercapto 4-butyramides, such as those described in the European Patent Application Publication No. EP-A-368 763; aminomercaptoalkyl amides, such as those described in the European Patent Application Publication No. EP-A-432 000 and alkylaminomercaptoalkylamides, such as those described in the European Patent Application Publication No. EP-A-514 282; and (2/3) hydroxy-2 propyl thioglycolate and hydroxy-2 methyl-1 ethyl thioglycolate-based mixture (67/33) described in the French Patent Application Publication No. FR-A-2 679 448.
In at least one embodiment, cysteine is used.
The at least one reducing agent can be present in an amount for each ranging from 0.5 to 10% relative to the total weight of the reducing composition, such as from 1 to 8% or from 2 to 7% by weight.
According to at least one embodiment, the at least one reducing composition is allowed to react for a period of time ranging from 1 to 50 minutes, for example for from 1 to 30 minutes.
During or after application of the at least one reducing composition, the keratin fibers are 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, for example, be conducted by using 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 disclosure ranges, for example, from 7.5 to 11, such as from 8 to 9.5.
The pH value of the reducing composition of the disclosure may be obtained and/or adjusted by adding at least one alkaline agent, 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 mixtures thereof; or at least one acidifying agent, such as for example hydrochloric acid, acetic acid, lactic acid, boric acid, citric acid and/or phosphoric acid.
For improving the cosmetic properties of the hair fibers or to reduce or prevent their damage, the at least one reducing composition used in the method of the disclosure may also comprise at least one cosmetic active agent.
The at least one cosmetic active agent can be chosen from 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 fatty alcohols, swelling agents and penetrating agents or agents intended to improve the efficiency of the at least one reducing agent; and 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; fragrances; preserving agents; stabilizers; and mixtures thereof.
In at least one embodiment, the at least one 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.
In one embodiment, the at least one cationic polymer is chosen from those comprising units containing primary, secondary, tertiary and/or quaternary amine groups, that either may belong to the polymer main chain, or are carried by a side substituent that is directly bound to it.
The at least one cationic polymer that can be used has generally a number average molecular weight ranging from 500 to 5×10⁶, for example from 103 to 3×10⁶.
In at least one embodiment, the at least one cationic polymer is chosen from polyamine, polyaminoamide and quaternary polyammonium type polymers.
These are known products. They are, for example, described in the French Patent Nos. 2 505 348 and 2 542 997. Examples of said cationic polymers include, but are not limited to:
(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one unit of following formulae (I), (II), (III) or (IV):
wherein:
R₃, being the same or different, is chosen from hydrogen atoms and CH₃radicals;
A, being the same or different, is chosen from linear or branched alkyl groups comprising from 1 to 6 carbon atoms, such as 2 or 3 carbon atoms, and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;
R₄, R₅, R₆, being the same or different, are chosen from alkyl groups comprising from 1 to 18 carbon atoms and benzyl radicals, for example alkyl groups comprising from 1 to 6 carbon atoms;
R₁and R₂, being the same or different, are chosen from hydrogen atoms and alkyl groups comprising from 1 to 6 carbon atoms, for example methyl or ethyl groups;
An anion X is optionally present, and when present is 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 further comprise at least one unit derived from comonomers that may be chosen from acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on a nitrogen atom with lower from (C₁-C₄)alkyl groups, acrylic or methacrylic acids or esters thereof, vinyl lactames, such as vinyl pyrrolidone or vinyl caprolactame, and vinyl esters.
Thus, these polymers of family (1) include, for example, but are not limited to:

- 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 European Patent Application No. A-080976, such as products marketed under the name BINA QUAT P 100 by CIBA GEIGY;
- copolymers of acrylamide and methacryloyloxyethyl trimethylammonium methosulfate, such as products 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, for example “GAFQUAT 734” or “GAFQUAT 755”, or products called “COPOLYMER 845, 958 and 937”. These polymers are also described in detail in French Patent Nos. 2 077 143 and 2 393 573;
- terpolymers of dimethylaminoethyl methacrylate, vinyl caprolactame and vinyl pyrrolidone, such as the product marketed under the name GAFFIX VC 713 by ISP;
- copolymers of vinyl pyrrolidone and methacrylamidopropyl dimethyl amine marketed, for example, 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, such as those described in the French Patent No. 1 492 597, and for instance, 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, for example, in U.S. Pat. No. 4,131,576, such as hydroxyalkyl celluloses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropyl celluloses graft, for example, with a methacryloylethyl trimethylammonium, methacryImidopropyl trimethylammonium, or a dimethyl diallylammonium salt.
The products marketed corresponding to this definition include, but are not limited to, products marketed under the name “Celquat L 200” and “Celquat H 100” by National Starch.
(4) Cationic polysaccharides, such as those described in U.S. Pat. Nos. 3,589,578 and 4,031,307, such as guar gums comprising trialkylammonium cationic groups. Guar gums modified with a 2,3-epoxypropyl trimethylammonium (e.g. chloride) salt may be used, for example.
Such products are marketed, for example, under the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by MEYHALL.
(5) Polymers comprising 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, for example, described in French Patent Nos. 2 162 025 and 2 280 361.
(6) Water-soluble polyaminoamides such as those prepared by polycondensing an acidic compound with a polyamine; these polyaminoamides may be crosslinked with an epihalohydrine, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrine, a bis-azetidinium, a bis-haloacyidiamine, 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 at least one tertiary amine functional group, quaternized. Such polymers are, for example, described in French Patent Nos. 2 252 840 and 2 368 508.
(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with 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 comprises from 1 to 4 carbon atoms and is chosen from methyl, ethyl and propyl groups. Such polymers are, for example, described in French Patent No. 1 583 363.
Examples of these derivatives include, but are not limited to, polymers of adipic acid, dimethylaminohydroxypropyl and diethylene triamine marketed under the name “Cartaretine F, F4 or F8” by Sandoz.
(8) Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratio of the polyalkylene polyamine to the dicarboxylic acid ranges from 0.8:1 to 1.4:1. The thus resulting polyaminoamide is reacted with epichlorhydrine according to a molar ratio of epichlorhydrine to the at least one secondary amine group of the polyaminoamide ranging from 0.5:1 to 1.8:1. Such polymers are, for example, described in U.S. Pat. Nos. 3,227,615 and 2,961,347.
Polymers of this type are, for example, 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 formulae (V) or (VI):
wherein k and t are 0 or 1, the sum k+t being equal to 1; R₉is chosen from hydrogen atoms and methyl radicals; R₇and R₈, independently from each other, are chosen from alkyl groups comprising from 1 to 22 carbon atoms, hydroxyalkyl groups wherein the alkyl group comprises from 1 to 5 carbon atoms, and lower amido(C₁-C₄)alkyl groups, or R₇and R₈may represent together with the nitrogen atom to which they are bound, heterocyclic groups, such as piperidinyl or morpholinyl; in one embodiment, R₇and R₈independently from each other represent an alkyl group comprising 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, for example, described in French Patent No. 2 080 759 and in related French Patent No. 2 190 406.
The previously defined polymers also encompass, for example, 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) Quaternary diammonium polymers comprising repeating units of formula (VII):
R₁₀, R₁₁, R₁₂and R₁₃, being the same or different, are chosen from aliphatic, alicyclic, or aryl aliphatic radicals comprising from 1 to 20 carbon atoms or lower hydroxyalkyl aliphatic radicals, or R₁₀, R₁₁, R₁₂and R₁₃, taken together or separately, form together with the nitrogen atoms to which they are bound heterocycles optionally comprising a second heteroatom different from nitrogen, or R₁₀, R₁₁, R₁₂and R₁₃represent a linear or branched, from C₁-C₆alkyl radical, substituted with a nitrile, ester, acyl, amide or —CO—O—R₁₄-D or —CO—NH—R₁₄-D group, where R₁₄is an alkylene and D a quaternary ammonium group;
A1 and B1 represent polymethylene groups comprising 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, at least one aromatic ring, or at least one oxygen or sulfur atom, or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester group, and
X⁻ represents an anion derived from a mineral or an organic acid;
A₁, R₁₀and R₁₂may 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 is chosen from:
a) glycol residues of formula: —O-Z-O—, where Z represents a linear or branched hydrocarbon radical or a group having one of the following formulae:
—(CH₂—CH₂—O)x-CH₂—CH₂— and
—[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)—
wherein x and y represent an integer ranging from 1 to 4 corresponding to a defined and unique polymerization degree, or any number ranging from 1 to 4 corresponding to a medium polymerization degree;
b) bis-secondary diamine residues, such as a piperazine derivative;
c) bis-primary diamine residues of formula: —NH—Y—NH—, wherein Y represents a linear or branched hydrocarbon radical, or the bivalent radical
—CH₂—CH₂—S—S—CH₂—CH₂—; and
d) ureylene groups of formula: —NH—CO—NH—.
In at least one embodiment, X⁻ is an anion chosen from chloride and bromide.
These polymers have a number average molecular weight generally ranging from 1000 to 100,000.
Such polymers are, for example, described in French Patent Nos. 2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 as well as in the U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.
In one embodiment, such polymers that may be used comprise repeating units of formula (VIII):
wherein R₁₀, R₁₁, R₁₂and R₁₃, being the same or different, represent alkyl or hydroxyalkyl radicals comprising from 1 to 4 carbon atoms, n and p are integers ranging from 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 maybe mentioned as a non-limiting example;
(11) Quaternary polyammonium compounds comprising repeating units of formula (IX):
wherein p represents an integer ranging from 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, and X⁻ is an anion;
Such polymers may be prepared according to methods described in the U.S. Pat. Nos. 4,157,388, 4,702,906, and 4,719,282. They are, for example, described in the European Patent Application No. EP-A-122 324.
Suitable examples thereof include, but are not limited to, “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(C₁-C₄) trialkyl(C₁-C₄)ammonium salts, such as polymers obtained by homopolymerizing dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerizing acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, where the homo- or copolymerization are followed with a crosslinking with an olefinically unsaturated compound, for example methylene bis acrylamide. In one embodiment, a crosslinked copolymer of acrylamide and methacryloyloxyethyl trimethylammonium chloride (20:80 by weight) may be used in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. Such dispersion is marketed, for example, under the trade name “SALCARE® SC 92” by ALLIED COLLOIDS. A crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride may also be used, comprising about 50% by weight of said homopolymer in mineral oil or in a liquid ester. Such dispersions are marketed, for example, under the trade names “SALCARE®) SC 95” and “SALCARE® SC 96” by ALLIED COLLOIDS.
Non-limiting examples of other cationic polymers to be suitably used in the context of the present disclosure are polyalkylene imines, such as polyethylene imines, polymers comprising vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrine, quaternary polyureylenes and chitin derivatives.
In at least one embodiment, the cationic polymer that is used in the context of the present disclosure, is 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 disclosure may vary from 0.01 to 10% by weight relative to the total weight of the composition, such as from 0.05 to 5% or from 0.1 to 3%.
As discussed above, the at least one cosmetic active agent that may be used in the composition of the disclosure may also be chosen from silicones.
In one embodiment, silicones that are optionally present in the reducing composition of the disclosure are 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.
The at least one silicone may be volatile or not.
In at least one embodiment, when they are volatile, the at least one silicone is chosen from those having a boiling point ranging from 60° C. to 260° C., and from:
cyclic silicones comprising from 3 to 7 silicon atoms, for example 4 or 5.
Suitable non-limiting examples thereof include octamethylcyclotetrasiloxane marketed, for example, under the trade names “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 or “SILBIONE 70045 V 5” by RHONE POULENC, and mixtures thereof.
Cyclocopolymers of the dimethyl siloxane and methylalkyl siloxane type may also be used, such as “SILICONE VOLATILE FZ 3109” marketed by UNION CARBIDE, having following chemical structure (X):
wherein “avec” means “with.”
Mixtures of cyclic silicones with organic compounds derived from silicon may also be used, 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′-trimethylsilyloxy)bis-neopentane mixture;
(ii) linear volatile silicones comprising from 2 to 9 silicon atoms and wherein the viscosity is lower than or equal to 5·10⁻⁶m²/s at 25° C., for example decamethyl tetrasiloxane marketed, for example, under the trade name “SH 200” by TORAY SILICONE. Non-limiting examples of 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.”
In one embodiment, non volatile silicones are used, such as polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, gums and silicone resins, polyorganosiloxanes modified with organofunctional groups, and mixtures thereof.
In another embodiment, these silicones are chosen from polyalkyl siloxanes, for example polydimethyl siloxanes with trimethylsilyl end groups having a viscosity ranging from 5·10⁻⁶to 2.5 m²/s at 25° C., for example from 1·10⁻⁵to 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 limiting 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, for instance, 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 as non-limiting examples, (called dimethiconol in the CTFA dictionary), such as fluids of 48 series from RHONE POULENC.
This polyalkyl siloxane class also includes, for example, products marketed under the trade names “ABIL WAX 9800 and 9801” by GOLDSCHMIDT which are (C₁-C₂₀) polyalkyl siloxanes.
In one embodiment, polyalkylaryl siloxanes are chosen from linear and/or branched, polydimethyl methylphenyl siloxanes, and polydimethyl diphenyl siloxanes with a viscosity ranging from 1·10⁻⁵to 5·10⁻²m²/s at 25° C.
Suitable non-limiting 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 PH1 000 products; and
- some fluids of SF series from GENERAL ELECTRIC, such as SF 1023, SF 1154, SF 1250, SF 1265.

Examples of silicone gums that may be present in the reducing composition of the disclosure include, but are not limited to, polydiorganosiloxanes having high number average molecular weights ranging from 200,000 to 1,000,000 used either alone or in combination in a solvent. In one embodiment, this solvent may be chosen from volatile silicones, polydimethyl siloxanes fluids (PDMS), polyphenylmethyl siloxane fluids (PPMS), isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecanes, and mixtures thereof.
As non-limiting examples, the following products may be mentioned:

- polydimethyl siloxane,
- polydimethyl siloxane/methylvinyl siloxane gums,
- polydimethyl siloxane/diphenyl siloxane,
- polydimethyl siloxane/phenylmethyl siloxane, and
- polydimethyl siloxane/diphenyl siloxane/methylvinyl siloxane.

Further non-limiting examples of products that may be used include the 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, which is a non-limiting example of an 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 of two PDMS with different viscosities, for example of a PDMS gum and a PDMS fluid, such as the SF 1236 product from GENERAL ELECTRIC, wherein SF 1236 is a mixture of an SE 30 gum as defined hereabove with a viscosity of 20 m²/s and an SF 96 fluid with a viscosity of 5·10⁻⁶m²/s. In one embodiment, such product comprises 15% of SE 30 gum and 85% of SF 96 fluid.
In one embodiment, organopolysiloxane resins optionally present in the oxidizing composition of the method of the disclosure are siloxane-based crosslinked systems comprising following units: R₂SiO_2/2, R₃SiO_1/2, RSiO_3/2and SiO_4/2, wherein R is chosen from hydrocarbon groups comprising from 1 to 16 carbon atoms and phenyl groups. In a further embodiment, R is chosen from lower C₁-C₄alkyl radicals, such as a methyl, and phenyl radicals.
Further non-limiting examples of 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, which are dimethyl/trimethyl siloxane-structured silicones.
In one embodiment, resins of the trimethyl siloxysilicate type marketed under the trade names X22-4914, X21-5034 and X21-5037 by SHIN-ETSU may be used.
Organomodified silicones optionally present in the reducing composition of the disclosure are chosen from silicones such as previously defined, which comprise in their structure at least one organofunctional group bound via a hydrocarbon radical.
Examples of organomodified silicones include, but are not limited to, polyorganosiloxanes comprising:
polyethyleneoxy and/or polypropyleneoxy groups optionally comprising from C₆-C₂₄alkyl 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 (C_1-2)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 Q2 8220 or DCZ-8566 and DOW CORNING 929 or 939 or DCZ-8299 or QZ7224 by DOW CORNING. In one embodiment, the substituted amine groups are chosen from C₁-C₄aminoalkyl groups and 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 French Patent Application No. FR-A-85 16334;
acyloxyalkyl groups, such as for example polyorganosiloxanes described in U.S. Pat. No. 4,957,732;
anionic groups of the carboxylic type, for example the products described in European Patent EP 186 507 from CHISSO CORPORATION, or of the alkyl carboxylic type, such as those present in the X-22-3701 E product from SHIN-ETSU; 2-hydroxyalkyl sulfonate; and 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 Patent Application No. EP 342 834, for example the Q2-8413 product from DOW CORNING.
In one embodiment, the at least one silicone is an amino silicone.
As discussed above, the method of the disclosure comprises an oxidizing composition applying step.
The at least one oxidizing composition comprises generally at least one oxidizing agent chosen from hydrogen peroxide, carbamide peroxide, alkaline bromates, polythionates, persalts, such as perborates, percarbonates and persulfates.
In at least one embodiment, the at least one oxidizing agent is hydrogen peroxide.
The at least one oxidizing agent is present in an amount ranging from 0.1 to 10% by weight relative to the total weight of the oxidizing composition, for example from 0.5 to 5%.
In one embodiment, when the at least one oxidizing agent represents hydrogen peroxide in aqueous solution, the at least one oxidizing composition used in the method of the disclosure comprises at least one hydrogen peroxide stabilizing agent.
Examples of stabilizing agents include, but are not limited to, 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. In one embodiment, at least one stannate is used alone or in combination with at least one pyrophosphate.
The at least one hydrogen peroxide stabilizing agent may be present in an amount ranging from 0.0001% to 5% by weight relative to the total weight of the at least one oxidizing composition, for example from 0.01 to 2%.
The pH value of the at least one oxidizing composition ranges from 1.5 to 4.5, for example from 2 to 3.5.
In at least one embodiment, the at least one oxidizing composition is allowed to react for a period of time ranging from 2 to 30 minutes, for example for from 2 to 15 minutes, or from 2 to 7 minutes.
In one embodiment, the method of the disclosure comprises applying a hair-care composition comprising at least one cationic polymer to the hair.
All the cationic polymers that have been described hereabove as regards to the reducing composition may be used in the hair-care composition.
In at least one embodiment, the at least one cationic polymer that is used in the context of the present disclosure is present in the at least one reducing composition comprising cyclopolymers, such as dimethyldiallylammonium chloride homopolymers marketed under the trade name “MERQUAT® 100” by MERCK, diquaternary ammonium polymers of formula (VIII) or of formula (IX) and MEXOMERE PO.
In at least one embodiment, the at least one silicone is WACKER BELSIL ADM LOG 1 silicone.
Additionally applying a hair-care composition may allow one 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 disclosure. The hair-care composition, such as defined hereabove may also allow one to protect the hair's artificial color
The at least one oxidizing composition and the at least one hair-care composition used in the method of the disclosure may also comprise at least one cosmetic active agent, such as those previously mentioned with respect to the at least one reducing composition.
In at least one embodiment, the vehicle for the reducing, oxidizing and hair-care compositions used in the method of the disclosure is an aqueous medium comprising water, which may additionally comprise at least one cosmetically acceptable organic solvent, which may, for example, 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. The at least one organic solvent may then be present in concentrations ranging from 0.1 to 20% by weight relative to the total weight of the composition, for example from 1 to 10%.
The pH value of the reducing composition, the oxidizing composition and/or the hair-care composition used in the method of the disclosure may be obtained and/or adjusted by adding either at least one alkaline agent, 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 be considered either alone or in combination; or at least one acidifying agent, such as for example hydrochloric acid, acetic acid, lactic acid, boric acid, citric acid and phosphoric acid.
The at least one reducing composition, the at least one oxidizing composition and/or the at least one hair-care composition used in the method of the disclosure may, independently from each other, be in the form of a lotion; a gel, thickened or not; a foam; or a cream.
As discussed above, the method of the disclosure comprises applying at least one reducing composition onto the keratin fibers, for example onto the hair, applying at least one oxidizing composition.
According to one embodiment of the disclosure, the application of the at least one reducing composition and/or the at least one oxidizing composition do(es) occur under heating or is (are) immediately followed with heating.
In one embodiment, the method of the disclosure further comprises, following the application of the reducing composition, and/or following the application of the at least one oxidation composition, with rinsing the keratin fibers with water.
In one embodiment, the at least one reducing composition may also be applied as the hair winding up is being performed. The at least one reducing composition may then be allowed to react for a time period ranging from 1 to 50 minutes, for example from 1 to 30 minutes.
It is also possible after having applied the at least one 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, for example, be conducted by using 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.
In a further embodiment, a rinsing operation of the keratin fibers is then optionally effected with water, and then is followed by a drying operation.
In at least one embodiment, the drying step is complete, and it may be done, for example, by using a domestic hair dryer or a hood hair dryer or a heating hair cap, or be effected by carefully wringing the hair out.
In one embodiment, the at least one oxidizing composition enabling one 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, for example with water, then the tensioning devices are removed.
As discussed above, the method of the disclosure may comprise applying to the hair a hair-care composition comprising at least one cationic polymer and/or at least one silicone, such as an amine silicone. As an example, the hair-care composition may be applied:
prior to setting the hair under tension,
between the hair tensioning and the application of the at least one reducing composition,
after the optional rinsing with water following the application of the at least one reducing composition and before the application of the at least one oxidizing composition, and/or
after rinsing with water following the application of the at least one oxidizing composition.
In one embodiment, the at least one hair-care composition is applied before mechanically setting the keratin fibers under tension. Thus, according to the present disclosure, mechanically setting the keratin fibers under tension may be carried out after applying at least one hair-care composition comprising at least one cationic polymer and/or at least one silicone, such as an amino silicone.
In one embodiment, the hair-care composition application is followed with a rinsing, such as a rinsing with water.
Also disclosed herein is a kit comprising:
tensioning devices, as previously described,
a first compartment comprising at least one cosmetic composition comprising at least one reducing agent, and
a second compartment comprising at least one cosmetic composition, comprising at least one oxidizing agent.
Other than in the examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, unless otherwise indicated the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
By way of non-limiting illustration, concrete examples of certain embodiments of the present disclosure are given below.

EXAMPLES

Example 1

A reducing composition and an oxidizing composition were prepared and implemented a method for permanently reshaping the hair according to the disclosure.
Formulations are as follows:

Composition Example

In the following composition examples, percentages are expressed by weight relative to the total weight of the composition.
Reducing Composition (1):


	Cysteine	4%
	Ammonium thioglycolate in	1.5%
	71% aqueous solution
	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 disclosure, as also as described in example 2. With the method of the disclosure, 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 colored hair was 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 disclosure did not deteriorate the artificial hair color.

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 was 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, comprising:

mechanically setting the keratin fibers under tension by winding the keratin fibers around at least one mechanical tensioning device so as to form a curl, wherein said device is flexible and closable upon itself;

applying onto the keratin fibers at least one reducing composition, so as to reduce the keratin disulfide bonds,

optionally rinsing the keratin fibers,

drying the keratin fibers, and

applying at least one oxidizing composition, to reform said bonds.

2. A method according to claim 1, wherein the at least one mechanical tensioning device is at least one curler or at least one curlpaper.

3. A method according to claim 2, wherein the at least one curler is a tulip-type curler.

4. A method according to claim 1, wherein the at least one reducing composition comprises, in a cosmetically acceptable medium, at least one reducing agent chosen from sulfites, bisulfites, thiols and phosphines.

5. A method according to claim 4, wherein the at least one reducing agent is chosen from L-cysteine, D-cysteine, L,D-cysteine, and the salts thereof; thiolactic acid, and the salts and esters thereof; and thioglycolic acid, and the salts and esters thereof.

6. A method according to claim 5, wherein the at least one reducing agent is present in an amount ranging from 0.5 to 10% by weight, relative to the total weight of the reducing composition.

7. A method according to claim 1, wherein the at least one reducing composition is left to stand for a time period ranging from 1 to 50 minutes.

8. A method according to claim 1, wherein the pH value of the at least one reducing composition ranges from 7.5 to 11.

9. A method according to claim 1, wherein the at least one oxidizing composition comprises at least one oxidizing agent chosen from hydrogen peroxide, carbamide peroxide, alkaline bromates, polythionates, persalts, percarbonates and persulfates.

10. A method according to claim 9, wherein the at least one oxidizing agent is present in an amount ranging from 0.1 to 10% by weight relative to the total weight of the oxidizing composition.

11. A method according to claim 1, wherein the at least one oxidizing composition is left to stand for a time period ranging from 2 to 30 minutes.

12. A method according to claim 1, wherein the pH value of the at least one oxidizing composition ranges from 1.5 to 4.5.

13. A method according to claim 1, further comprising, following the application of the at least one reducing composition and/or following the application of the at least one oxidizing composition, with rinsing the keratin fibers with water.

14. A method according to claim 1, wherein the application of the at least one reducing composition is effected under heating or is immediately followed with a heating operation.

15. A method according to claim 1, wherein the at least one reducing composition and/or the at least one oxidizing composition are, independently of each other, in a form chosen from a lotion, thickened or not thickened; a cream; a gel; and a foam.

16. A method according to claim 1, wherein the mechanically setting the keratin fibers under tension occurs after applying at least one hair-care composition which comprises at least one cationic polymer and/or at least one silicone.

17. A method according to claim 16, wherein the application of the at least one hair-care composition is followed by rinsing.

18. A multi-compartment kit, comprising:

at least one mechanical tensioning device, wherein said at least one device is flexible and closable upon itself,

a first compartment comprising at least one cosmetic composition comprising at least one reducing agent, and

a second compartment comprising at least one cosmetic composition, which comprises at least one oxidizing agent.