FR2858551A1 - Permanent deformation of hair comprises applying a reducing composition containing sufficient metal and/or ammonium ions to precipitate an anionic or amphoteric polymer in situ - Google Patents

Abstract

Permanent deformation of hair comprises applying an aqueous solution of an anionic or amphoteric polymer, applying a reducing composition containing sufficient metal and/or ammonium ions to precipitate the polymer in situ, shaping the hair, allowing the reducing composition to act, applying an oxidizing composition, allowing the oxidizing composition to act, and rinsing the hair. An independent claim is also included for a multicomponent product for permanent deformation of hair, comprising a solution of an anionic or amphoteric polymer in a medium containing water and optionally a solvent; a reducing composition comprising a reducing agent capable of cutting keratin disulfide bonds and sufficient metal and/or ammonium ions to precipitate the polymer; and an oxidizing composition comprising an oxidizing agent capable of reestablishing keratin disulfide bonds.

Description

A method of permanently deforming the hair comprising a step of

  in situ precipitation of anionic or amphoteric polymer

  The present invention relates to a permanent hair deformation process comprising a step of in situ precipitation of a water-soluble polymer, and a multi-component agent for carrying out such a method.

  One of the techniques commonly used to obtain a permanent deformation of the hair is to treat them successively with a reducing agent capable of cutting the disulfide bridges of the keratin, then with an oxidizing agent restoring disulfide bridges while maintaining the hair under a mechanical stress, for example by means of curlers.

  The traction exerted by the curlers makes it possible to obtain a detachment of roots, but also involves the waving of the hair. However, many women want to increase the volume of their hair without having curly hair.

  While it is possible to use large hair curlers to soften the curly aspect and simply obtain a slight undulation, the holding of such permanent deformations is not very good.

  Another disadvantage of the usual permanent deformation techniques is the sensitization of the hair resulting from the repeated treatment of the hair with strong reducing and oxidizing agents.

  To overcome this disadvantage, it has already been proposed to use gelling reductive compositions for locating the product at the roots and thus avoid chemical degradation of the hair along its length. The use of a gelled reductive composition does not, however, dispense with the step of winding the hair on hair curlers and this technique therefore remains long and difficult to implement by the user himself and gives a result. of little lasting deformation.

  There are a number of attempts to achieve permanent hair deformation without the use of mechanical shaping means such as curlers. Thus, the application WO99 / 18922 discloses a method of permanent deformation of the hair using a thickened reducing composition having a moderate tackiness. This reducing composition makes it possible to shape the hair without applying a stress of tension. The oxidizing composition is applied directly to the hair treated with the reducing composition, without intermediate rinsing to remove the reducing agent. This document does not envisage at any time the partial deformation of the hair, limited to certain areas, for example to the zone near the roots.

  The application WO01 / 95868 discloses a permanent hair deformation process limited to certain areas, for example that close to the roots, not using mechanical means of tensioning the hair such as curlers. Maintaining the shape imposed on the hair during the reduction and oxidation phases is provided by the reducing composition itself which contains a wax, absorbent hydrophilic particles, particularly flour particles, and a reducing agent absorbed by hydrophilic particles. This process is relatively complex since it involves melting the wax in a suitable heating device and mixing the melted wax with the absorbent hydrophilic particles and the reducing agent. The application of the hot mixture on the hair requires the hairdresser a certain dexterity and is difficult to achieve by the user himself. On the other hand, relatively high color stripping is observed when this technique is used for the permanent deformation of colored hair.

  The Applicant has developed a new method of permanent hair deformation, substantially easier to implement than that described in WO01 / 95868, and which does not require prior preparation of the reducing composition by means of a device heater. In the process of the present invention, maintaining the shape imposed on the hair during the reduction and oxidation steps is ensured not by the solidification of a fluid or malleable substance, but by the precipitation in situ of a polymer applied to the hair in the form of a solution.

  This method is surprisingly easy, simply involving the successive application of three compositions (polymer composition, reducing composition and fixing composition) and manual shaping of the hair requiring no mechanical means of powering up.

  The present invention therefore relates to a permanent deformation process of the hair, comprising, in order, the following steps: (a) application, on the zones to be deformed, of a solution of an anionic or amphoteric polymer in a medium containing water and, optionally, one or more cosmetically acceptable solvents; (b) applying, on the zones treated in step (a), a reducing composition containing a reducing agent capable of cutting the bridges disulphide keratin and a sufficient amount of metal cations and / or ammonium ions to precipitate in situ the anionic or amphoteric polymer, (c) shaping the hair so treated followed by a laying time of the reducing composition (d) applying, to the areas treated in steps (a) and (b), a fixing composition containing an oxidizing agent, followed by a setting time of the oxidizing composition, and (e) rinsing the hair .

  The invention also relates to a multi-component agent for the permanent deformation of the hair comprising, * as the first component (component A), a solution of an anionic or amphoteric polymer in a medium containing water and, optionally, one or more cosmetically acceptable solvents, capable of forming a solid precipitate in the presence of a sufficient amount of metal cations or ammonium ions, * as a second component (component B), a reducing composition containing a reducing agent capable of cleaving the disulfide bridges of keratin, and a sufficient amount of metal cations and / or ammonium ions to precipitate the anionic or amphoteric polymer of the first component, and as a third component (component C), a oxidizing composition containing an oxidizing agent capable of restoring the disulfide bridges of keratin.

  This multi-component agent is preferably in the form of a multi-compartment kit comprising at least three compartments respectively containing the three components A, B and C above, packaged and sold in one package. The cosmetically acceptable organic solvents which can be used in the present invention to dissolve the anionic or amphoteric polymer are liquids at room temperature and at atmospheric pressure. These solvents are preferably monoalcohols, polyols or ethers of these alcohols or polyols. There may be mentioned, for example, ethanol, isopropanol, glycerol, propylene glycol or propylene glycol monomethyl ether. Ethanol is a particularly preferred solvent.

  The anionic or amphoteric polymer solution (component A) can be in a thickened or even gelled form, allowing a targeted application at certain areas of the hair.

  The anionic or amphoteric polymers used in component A of the present invention are soluble in the liquid medium used. Without wishing to be bound by any theory, the Applicant believes that after application of the polymer solution to the hair, the ionic strength of the medium is greatly increased by the addition of the reducing composition which is heavily loaded with metal cations and / or ammonium ions. (in the form of salts). There is then a contraction of the macromolecular ball resulting ultimately in the precipitation of the polymer.

  The ionic strength necessary to obtain the in situ precipitation of the polymer depends on a number of factors such as the number of charges of the polymer, the more or less hydrophobic nature of the polymer in its unfilled form, the molecular weight of the polymer, the concentration of the polymer in the component (A) or the pH of the medium obtained by in situ mixing of the components (A) and (B).

  This ionic strength can be brought by inorganic or organic salts present in the reducing composition B, but also by the reducing agent itself when it is in salt form.

  The Applicant has found that a concentration of metal and / or ammonium cations in the applied reducing composition (component (B)) greater than 0.3 M was generally sufficient to obtain a deposit of precipitated polymer of a satisfactory quality allowing the 10 maintaining the shape of the hair during the reduction and oxidation steps. Preferably, this concentration is between 0.5 and 6 M. In principle, it is possible to use any anionic or amphoteric polymer, natural or synthetic.

  A family of preferred polymers that can be used for the process of the invention is formed by synthetic copolymers obtained by polyaddition of a mixture of anionic monomers and of nonionic monomers, or by polyaddition of a mixture of anionic, nonionic and cationic monomers.

  The anionic monomers used for the synthesis of such copolymers are, for example, acrylic acid, methacrylic acid, acrylamido-2-methylpropanesulphonic acid, crotonic acid and itaconic acid, or a mixture of these acids.

  Nonionic monomers include, for example, C 1-4 alkyl acrylates and methacrylates, acrylamide, vinyl acetate, vinyl para-tert-butylbenzoate, methacrylamide, N-monoalkyl C, 8 -acrylamides, N-vinylformamide, N-vinylacetonamide, hydroxypropyl acrylate and hydroxypropyl methacrylate.

  The cationic monomers used in combination with the anionic and nonionic monomers for the synthesis of amphoteric copolymers which can be used in the present invention are chosen, for example, from di (C 1-4 alkyl) diallylammonium salts and compounds of formula ( Embedded image in which R 1 represents a hydrogen atom or a methyl group, R 2 and R 3, which may be identical or different, each represent a hydrogen atom or a C 1 -C 6 alkyl group; 4 is linear or branched, R 4 is hydrogen, straight or branched C 1-4 alkyl or aryl, D is the following: wherein Y is amide, ester, urethane or urea, represents a linear, branched or cyclic C 1-10 -alkenene group which may be substituted or interrupted by a divalent aromatic or heteroaromatic ring, or which may be interrupted by a heteroatom selected from O, N, S and P, and having a ketone, amide, ester, urethane or urea function, n is 0 or 1, and X- represents anionic counterion such as a halide or sulfate ion.

  By way of examples of preferred copolymers, mention may be made of copolymers of (meth) acrylic acid and of C 1 -C 6 alkyl (meth) acrylate (INCI name: Acrylates Copolymer), marketed for example under the name Amerhold DR. By the company AMERCHOL, copolymers of vinyl acetate, vinyl para-tert-butylbenzoate and crotonic acid (INCI name: VA / Vinyl Butyl Benzoate / Crotonates Copolymer), sold for example under the name Mexomer PW by the company CHIMEX, or * the copolymers of octylacrylamide, tertbutylaminoethyl methacrylate and one or more monomers selected from acrylic acid methacrylic acid and C1-6 alkyl esters of these acids (name INCI: Octylacrylamide / Acrylates / Butylaminoethyl Methacrylate Copolymer) sold, for example, under the name Amphomer by the company National Starch.

  The anionic or amphoteric polymers that can be used in the present invention are however in no way limited to the copolymers obtained by polyaddition as described above. It is also possible to envisage the use of polycondensates such as polyesters, polyamides or polyurethanes, or of copolymers and derivatives thereof such as silicone copolymers, bearing a sufficient number of anionic charges and possibly cationic charges to be soluble in the liquid medium of the component (A) and sufficiently hydrophobic to form a solid precipitate in case of increase of the ionic strength.

  Examples of this type of polymer are the Luviset Si-PURA product (Proposed INCI name: Polyurethane-6), marketed by BASF Aktiengesellschaft, which is a neutralized silicone polyurethane, in aqueous-alcoholic solution, resulting from polycondensation of isophthalic acid, adipic acid, hexylene glycol, neopentyl glycol, dimethylolpropionic acid, isophorone diisocyanate and bis-ethylaminoisobutyldimethicone, or the product marketed by AMERCHOL under the name Viscophobe DB 1000 (INCI name: Polyacrylate-3).

  The anionic or amphoteric polymer is preferably present in the solution of component A in a concentration sufficient to allow the formation of a precipitated polymer deposit capable of stiffening the keratinous fibers for the time necessary for the destruction and reconstruction of the disulfide bridges of the keratin. A satisfactory amount and quality of precipitate is generally obtained for an anionic or amphoteric polymer concentration of at least 5%, preferably between 7 and 30% by weight, relative to the total weight of the solution applied in the stage. (at).

  To increase the ionic strength of the reducing medium to a sufficient value, any organic or inorganic salt which does not interfere with the disulfide bond reduction reaction can be used in principle.

  Particularly preferred are ammonium salts and alkali metal salts.

  When the cations are provided by the reducing agent (in salt form) this comprises one or more carboxylate functions. By way of example, mention may be made of ammonium thioglycolate or ammonium thiolactate.

  The metal or ammonium cations can also come from mineral hydroxides. As examples of usable inorganic salts, mention may be made of alkali metal halides such as sodium chloride.

  The organic salts may be, for example, ammonium citrate, and the inorganic hydroxides may be sodium hydroxide (NaOH) or ammonia (NH 4 OH).

  The reduction step of the process of the present invention is preferably carried out at a pH of between 7 and 11, in particular between 7.5 and 9.5.

  Those skilled in the art will be able to choose, by virtue of their general technical knowledge, the appropriate pH adjusting agents and buffering agents to adjust the pH of components A and B to a suitable value.

  The reducing agent of the reducing composition may be any known reducing agent selected from those customarily used in the field of permanent hair deformation, such as sulphites, bisulphites and thiols. Among these reducing agents, cysteine, cysteamine, thiolactic acid and thioglycolic acid and cosmetically acceptable salts thereof, in particular ammonium thioglycolate, are particularly preferred.

  The concentration of this reducing agent in the reducing composition is preferably between 1% and 25% by weight, in particular between 1 and% by weight.

  After application of the reducing composition loaded with metal and / or ammonium cations (in the form of inorganic or organic salts) and precipitation of the polymer, the hair is given the desired shape by simply using the hands or simple mechanical means to maintain easily place longer locks of hair, such as forceps, combs, barrettes, strands and elastics. This implementation can be performed by the user himself and does not require the intervention of a hairdresser.

  The reducing agent is then allowed to act for a time sufficient to achieve the desired reduction. This exposure time is preferably between 2 and 30 minutes, and in particular between 5 and 15 minutes.

  It is possible to insert between the reduction step (c) and the oxidation step (d) an intermediate rinsing step. However, it should be ensured that this rinse leaves a sufficient amount of precipitate to impose the hair shape during the oxidation step.

  In a preferred embodiment of the present invention, the method does not include an intermediate rinsing step (between the reduction step (c) and the oxidation step (d)). Such rinsing could indeed weaken or eliminate the deposit of precipitated polymer, thus destroying the shaping of the hair during the fixing step.

  The fixing composition is therefore preferably applied to the hair directly after the first exposure time. This application is of course as far as possible without changing the shape imposed on the hair in the previous step. Such an application can be done for example using an aerosol device dispensing a fixing foam or small droplets of a fixing solution. The nature of the oxidizing agent used in this fixing composition is not critical for the present invention and any known oxidizing agent usually used for the oxidation of hair, such as hydrogen peroxide, can be used. urea peroxide, bromates, persalts and mixtures thereof.

  The exposure time for the fixing step is generally between 2 and 30 minutes, preferably between 2 and 15 minutes.

  The remaining composition on the hair is then removed by rinsing, followed optionally by washing and / or other hair treatment.

  Each of the three compositions of the multicomponent agent may further contain active ingredients and cosmetic adjuvants commonly used in the hair field. These additives are chosen for example from vitamins, amino acids, oligopeptides, peptides, hydrolysed proteins or not, modified or not, enzymes, acids and branched or unbranched fatty alcohols, animal waxes, vegetable or mineral, ceramides and pseudo-ceramides, hydroxylated organic acids, UV filters, anti-oxidants and anti-free radical agents, chelating agents, anti-dandruff agents, seborrhea regulating agents, soothing agents, cationic, anionic, nonionic or amphoteric surfactants, cationic, anionic, neutral or amphoteric polymers, organomodified or non-organomodified silicones, mineral, vegetable or animal oils, polyisobutenes and poly (olefins), fatty esters, hair dyes such as direct dyes and pigments The following example illustrates a multicomponent agent for the deformation of hair x.

Example 15

  Component A Luviset Si-P.U.R.A Demineralized water 66.6 g q.s. 100 g Component B Thioglycolic acid 5.1 g Pentasodium salt of diethylenetriaminopentaacetic acid 0.4 g Ammonia 5.6 g Ammonium chloride 5.0 g Hydroxypropylguar 0.8 g Mexomere PO * (Chimex) 1.6 g Tegobetaine HS ** (Goldschmidt) 1.4 g Ammonium dithiodiglycolate 1.6 g Glycerol 3.0 g Perfume, peptizer qs

  Demineralized water q.s. 100 g * polymer of N, N, N, N-tetramethylhexamethylenediamine and trimethylene chloride (INCI: Hexadimethrin Chloride) ** cocamidopropylbetaine and glycerol laurate Component C (fixing composition) Hydrogen peroxide in solution at 50% Stabilizers Laurylsulfate Ammonium Citric acid Fragrance, peptizer Demineralised water 4.8 g 0.03 g 4.0 g qs pH 3 q.s.

  q.s. 100 g These three components were used in accordance with the method of the present invention for permanent hair deformation. On all models, the treated hair has texture and mass. They are easy to style, modelable and bulky.

  The cosmetic effects observed are preserved durably during a large number of shampoos.

  When the method of the present invention is used on hair which has previously undergone hair coloration, it does not suffer from permanent deformation treatment.

Claims (21)

  1. A method of permanent deformation of the hair, comprising, in order, the following steps: (a) application, on the zones to be deformed, of a solution of an anionic or amphoteric polymer in a medium containing water and, optionally, one or more cosmetically acceptable solvents, (b) applying, on the zones treated in step (a), a reducing composition containing a reducing agent capable of cutting the disulfide bridges of keratin and a quantity sufficient metal cations and / or ammonium ions to precipitate in situ the anionic or amphoteric polymer, (c) shaping the hair so treated followed by a laying time of the reducing composition, (d) application, on the zones treated in steps (a) and (b), a fixing composition containing an oxidizing agent, followed by a setting time of the oxidizing composition, and (e) rinsing the hair.   2. Method according to claim 1, characterized in that it further comprises, between step (c) and step (d), an intermediate rinsing step leaving a sufficient amount of precipitate to impose the hair a shape during the oxidation step (d).   3. Method according to claim 1 or 2, characterized in that the anionic polymer is a synthetic copolymer obtained by polyaddition of a mixture of anionic monomers and nonionic monomers.   4. Method according to claim 1 or 2, characterized in that the amphoteric polymer is a synthetic copolymer obtained by polyaddition of a mixture of anionic monomers, nonionic monomers and cationic monomers.   5. Method according to claim 3 or 4, characterized in that the anionic monomers are selected from acrylic acid, methacrylic acid, acrylamido-2-methylpropanesulfonic acid, crotonic acid and itaconic acid.   6. Process according to any one of claims 3 to 5, characterized in that the nonionic monomers are chosen from C1-4 alkyl acrylates and methacrylates, acrylamide, vinyl acetate, vinyl acetate, vinyl para-tert-butylbenzoate, methacrylamide, N-mono- (C 1-8 alkyl) -acrylamides, N-vinylformamide, N-vinylacetonamide, hydroxypropyl acrylate and hydroxypropyl methacrylate.   7. Process according to Claims 4 to 6, characterized in that the cationic monomers are chosen from the di (C 1-4 alkyl) diallylammonium salts and the compounds of formula (I) R 1 (I) D, R 2 Wherein R 1 is hydrogen or methyl, R 2 and R 3, which may be identical or different, each represents a hydrogen atom or a linear or branched C 1-4 alkyl group, R 4 represents a hydrogen atom, a linear or branched C 1-4 alkyl group or an aryl group, D represents the following unit Y 3 A wherein Y represents an amide, ester, urethane or urea function, A represents a linear C 1-10 alkyene group , branched or cyclic, which may be substituted or interrupted by a divalent aromatic or heteroaromatic ring, or which may be interrupted by a heteroatom selected from O, N, S and P, and which may comprise a ketone, amide, ester, urethane or urea function , n is 0 or 1, and X 'r This is an anionic counterion such as a halide or sulfate ion.   8. Process according to any one of the preceding claims, characterized in that the anionic or amphoteric polymer is a copolymer of (meth) acrylic acid and (C 1 -C 6) alkyl (meth) acrylate, a copolymer of vinyl / vinyl para-tert-butylbenzoate / crotonic acid or an octylacrylamide copolymer of tert-butylaminoethyl methacrylate and one or more monomers selected from acrylic acid, methacrylic acid and C 1 -C 6 alkyl esters of these acids .   9. Process according to claim 1 or 2, characterized in that the anionic or amphoteric polymer is a polycondensate.   10. The method of claim 9, characterized in that the anionic or amphoteric polymer is a polyurethane, optionally silicone.   11. Process according to any one of the preceding claims, characterized in that the concentration of the anionic or amphoteric polymer in the solution applied in step (a) is at least 5%, preferably between 7 and 30% by weight, based on the total weight of this solution.   12. Method according to any one of the preceding claims, characterized in that the metal cations and / or ammonium ions are introduced by adding a mineral or organic salt or a hydroxide, or are provided by the agent. reducer when in the form of salt.   13. Process according to any one of the preceding claims, characterized in that the concentration of the metal and / or ammonium cations in the reducing composition is greater than 0.3 M, preferably between 0.5 and 6 M. 14. Process according to any one of the preceding claims, characterized in that the reducing agent is chosen from sulphites, bisulphites and thiols.   15. Process according to claim 14, characterized in that the reducing agent is chosen from cysteine, cysteamine, thiolactic acid and thioglycolic acid and cosmetically acceptable salts thereof, in particular thioglycolate. ammonium.   16. Method according to one of the preceding claims, characterized in that the concentration of the reducing agent in the reducing composition is between 1% and 25% by weight, preferably between 1 and 10% by weight.   17. Method according to any one of the preceding claims, characterized in that the exposure time of the reducing solution is between 2 and 30 minutes, preferably between 5 and 15 minutes.   18. Process according to any one of the preceding claims, characterized in that the oxidizing agent in the fixing composition is chosen from hydrogen peroxide, urea peroxide, bromates, persalts and mixtures of those -this.   19. Method according to any one of the preceding claims, characterized in that the exposure time of the fixing composition is between 2 and 30 minutes, preferably between 2 and 15 minutes.   20. Multicomponent agent for the permanent deformation of hair comprising, as first component (component A), a solution of an anionic or amphoteric polymer in a medium containing water and, optionally, one or more cosmetically acceptable solvents capable of forming a solid precipitate in the presence of a sufficient amount of metal cations or ammonium ions, * as a second component (component B), a reducing composition containing a reducing agent capable of cleaving the disulfide bridges; keratin, and a sufficient amount of metal cations and / or ammonium ions to precipitate the anionic or amphoteric polymer of the first component, and * as the third component (component C), an oxidizing composition containing an oxidizing agent capable of restore the disulfide bridges of keratin 21. Multi-component agent according to claim 18, characterized in that it is in the form of a multi-compartment kit comprising at least three compartments containing respectively the three components A, B and C.