FR2838051A1 - Method of permanent waving of hair in which the reMethod of permanent waving of hair in which the reducing or fixing composition contains a catalytic ducing or fixing composition contains a catalytic system comprising a manganese (II)or zinc (II) salsystem comprising a manganese (II)or zinc (II) salt and an alkali metal bicarbonate t and an alkali metal bicarbonate - Google Patents

Abstract

Method of permanent waving of human hair comprises application of reducing composition to tensioned hair, rinsing, fixing by contact with air or with a fixing solution and re-rinsing, in which the reducing composition comprises aminated acid with thiol group and the reducing solution comprises a catalytic system of manganese and/or zinc salt and/or oxide and alkali metal bicarbonate. Method of permanent waving of human hair by applying a reducing composition to tensioned hair, rinsing, optionally removing the means of tensioning, fixing by contact with air or with a fixing solution and re-rinsing, in which the reducing composition comprises an aminated acid with a thiol group and the reducing or fixing solution comprises a catalytic system comprising a manganese and/or zinc salt and/or oxide and an alkali metal bicarbonate. The molar concentrations of Mn(II) and or Zn(II) salt or oxide and the alkali metal bicarbonate in the reducing and/or fixing compositions are such that (Mn(II)) or (Zn(II)) or (Mn(II)+Zn(II))/HCO3 is less than or equal to 1.

Description

thiolactones. The invention relates to a method for treating fibers.

  keratin, in particular of the hair, with a view to obtaining a permanent deformation of

  - the latter, especially in the form of permed hair.

  We know that the most common technique for obtaining permanent deformation of the hair consists, firstly, in opening the disulfide bonds -SS- of keratin (cystine) by applying to the hair previously put under tension (curlers). and others) a composition containing a reducing agent (reduction step) then, after having rinsed the hair thus treated, to reconstitute in a second step said disulfide bonds by applying to the hair still under tension an oxidizing composition (oxidation step , also called fixing) so as to finally give the hair the desired shape. This technique thus makes it possible to carry out either the waving of the hair, or their straightening or their cutting. The new form imposed on the hair by a chemical treatment such as the above is eminently durable over time and resists in particular the action of washing with water or with shampoos, and this in contrast to simple conventional techniques of deformation:

  ternporaries, such as styling.

  o The reducing compositions which can be used for the implementation of the first step of such a conventional permanent hair deformation process (two-step process) generally contain, as reducing agents, sulfites, bisulfites, alkyl- phosphines or preferably

thiols.

  Among these, those commonly used are cysteine and its various derivatives, cysteamine and its derivatives, thiolactic acid, thioglycolic acid and its esters, in particular glycerol monothioglycolate. In this regard, and although having an unpleasant odor, so thioglycolic acid is particularly effective, and thus constitutes the compound of

  permanent reference to reduce keratin bonds.

  Usually, the keratinous material is wound on rollers and the reducing composition is applied to the latter for a time which can range from 2 to 40 minutes in order to allow the reducing agent time to act on the hair. The keratin material is then thoroughly rinsed. The following stage constitutes the second stage of a conventional process for permanent deformation of a keratinous material and consists in applying s to the latter an oxidizing or fixing composition in order to fix "the

  keratinous material or the hair according to the desired shape.

  With regard to the oxidizing compositions necessary for carrying out this fixing step, use is most often made in the

  practical, to compositions based on ox, vgenated water or alkaline bromates.

  o These compositions are applied to the keratinous material wound on the rollers for a relatively long time (fixation) of up to 30 minutes. They are generally in the form of very liquid lotions which it is difficult to contain the application to the only keratin fiber. It therefore happens that an excess of these compositions flows for example along the neck of the

   5 client making this step particularly unpleasant for the latter.

  After this operation, the keratin fiber is a last abundantly

- - - rinsed .: -; - - -

  Such a process certainly makes it possible to obtain permed hair having a fine curl, but it has a certain number of disadvantages: it is long and tedious for the one who implements it and very

  uncomfortable for the person who experiences it.

  In order to remedy some of these inconveniences, and with the aim of simplifying the operations of perms in general, new perm processes have been developed which are called self-regulating K perms. In these processes, the reducing composition generally comprises, in addition to the conventional reducing agent similar to that used: in a conventional process of permanent deformation (sulfites, thiols), a disulfide which is in excess compared to the conventional reducing agent and whose role is to oxidize the remains -SH released by the reduction of cystine and thus instantly reconstitute cystine bonds. The advantage of these

  process is to make it optional, and preferably unnecessary (permanent self-

  neutralizing), the fixing step and therefore the application with pause time of the oxidizing composition. These perms are done in one go. This results in better comfort for the client (the process is much more

  quick) as well as ease of use for the hairdresser.

  However, it should be noted that the crimp obtained by such methods is very often insufficient and that it degrades very quickly over time. In addition, since the fixing step is nonexistent, it remains long after and even after shampooing, an unpleasant odor due to excess

. -. -....

  reduced hair. In addition, to be effective, the reducing compositions must have high pH, generally greater than 9. These compositions, of high pH, have the major drawback that their repeated application to the hair

  can induce weakening of the hair.

  o The present invention aims in particular to solve the above problems. More specifically, its purpose is to propose a new process for treating permanent deformation of keratin fibers which is simple, rapid and comfortable for the client, or at least as effective, or even superior in terms of permanent deformation, as the conventional processes.

  and be less aggressive than these.

  The applicant has just discovered that if a process is used in which at least one of the reducing or fixing compositions comprises a catalytic system containing at least one salt or oxide of Mn (ll) and / or Zn (ll) and at least one alkali metal hydrogencarbonate, a process for treating keratin fibers is obtained which is simple, rapid, not very aggressive and which leads to significant and lasting permanent deformation,

  even after rinsing the keratin fibers.

  In addition, the Applicant has also discovered that if the reducing composition contains such a catalytic system, the step of fixing the keratin fibers can then be carried out in the open air in contact with the oxygen in the air without it is necessary to apply a fixing composition, and a fortiori a fixing composition containing agents

  oxidants such as hydrogen peroxide for example.

  It is known from the state of the art to carry out permanent hair deformation processes in the presence of metal salts of

  transition, including manganese.

  Thus, French patent FR-A-1 505 992 describes a process for pre-treating hair which must subsequently undergo styling, said process consisting of a chemical process analogous to that of a perm but without subjecting the hair to mechanical deformation (no curlers or rollers). The styling, carried out on

  hair thus treated has better qualities and better hold.

  The fixing step of said process can be carried out in the absence of an agent

......

  an oxidant, such as hydrogen peroxide, by adding manganese salts to the reducing composition; these have the effect of catalyzing the oxidation into

presence of oxygen in the air.

  Some of these permanent hair deformation processes carried out in the presence of transition metal salts, and in particular of manganese salts, make it possible to dispense with the use of a composition.

  classic oxidant, based on hydrogen peroxide for example.

  Thus, US Pat. No. 2,540,980 describes a treatment of the hair with a manganese salt in a process of permanent deformation. Manganese salt acts as an oxidation catalyst with oxygen in the air. This process makes it possible to dispense with a fixing step involving the use of a fixing agent of the hydrogen peroxide type. Said treatment consists either in - -: a pretreatment of the hair with the manganese salt before applying the reducing composition, or in applying the reducing composition

containing a manganese salt.

  o Similarly, French patent application FR2727 314 describes a new treatment process for the permanent deformation of keratin materials, in particular of the hair, of the type comprising a reduction phase and an oxidation phase, the reduction phase being carried out by applying to the keratinous material to be treated a reducing composition s containing at least one thiol, the keratinous material being impregnated with at least one manganese salt (preferably manganese dichloride) ... - - before / or during the reduction stage. This process is characterized by the fact that the keratinous material is treated, during or after the reduction phase and before the oxidation phase, in the presence of at least one agent o neutralizing the activity of the manganese salt. Such a method makes it possible to avoid a difference in coloration between the permed hair and the non-permed regrowth hair linked to the application of manganese salts on the hair during perm operations and with their even residual presence on the hair. Such a method also makes it possible to obtain a homogeneous coloration when it is applied to previously permed hair. The oxidation step in this process can be carried out by the application of a conventional oxidizing composition such as a composition based on hydrogen peroxide, or based on an alkali bromate, a parsley, a polythionate or a mixture of alkaline bromate and parsley, or even ..... allowing the oxygen in the air to act. None of these documents describes a process using the

  catalytic system of the invention.

  However, the patents EP-O 022 996-B1 and US 4,532,950 describe a process for the permanent deformation of the hair, in which the hair is first treated with a deformation product, it is kept in the desired form, the case if necessary it is rinsed, then it is treated with a fixing product. The deformation product is a mixture of two components 1 and 2, component 1 containing a substance reducing the keratin of the hair, such as for example a mercaptan compound (in particular a thioglycolic or thiolactic acid), and component 2 containing at least one organic compound chosen from activated double bond carboxylic acids and activated triple bond carboxylic acids, and optionally redox catalysts such as transition metal salts, such as manganese, iron and copper. In such a process, the oxidation step is carried out by applying a conventional oxidizing composition such as a 2% solution of hydrogen peroxide. According to Example 1 of US 4,532,950 and EP-O 022 996-B1, the reduction step of the process is carried out using a reduction composition whose compound 1 contains thioglycolic acid and a hygrogenocarbonate of ammonium, and of which compound 2

  s contains dilithium fumarate and hydrated manganese sulfate.

  However, the compound comprising at least one thiol group (thioglycolic acid) contained in the reduction composition is not an amino acid. In addition, patents EP-O 022 996-B1 and US 4,532,950 do not teach a deformation process which makes it possible to dispense with a step of its fixation requiring the use of a fixing agent of the peroxide type. 'hydrogen. Thus, the subject of the present invention is a new process for treating keratinous fibers, in particular hair, with a view to obtaining permanent deformation of the latter, in particular in the form of permanent hair, said process comprising the following steps : (i) applying a reducing composition to the keratin fibers to be treated, the keratin fibers being tensioned using means (rollers) used before, during or after said application; (ii) rinse the keratin fibers; (iii) optionally removing the tensioning means used in step (i) from the keratin fibers; (iv) fix the keratin fibers: - either directly by bringing said fibers into contact with air oxygen, - or by applying to said fibers a fixing composition; (v) separating the tensioning means if they were not in step (iii) and, optionally, (vi) rinsing the keratin fibers again, said process being characterized in that: (vii ) the reducing composition comprises, in a physiologically acceptable vehicle, an effective amount of at least one

  amino acid comprising at least one thiol group, and - -

  (viii) at least one of the reducing and fixing compositions comprises, o in a physiologically acceptable vehicle, a catalytic system of at least one eVou salt or Mn (II) oxide of Zn (II) and at least one alkali metal hydrogen carbonate, the proportions of salt eVou oxide of Mn (ii) eVou of Zn (II) and of alkali metal hydrogen carbonate being such that: [(II)] [Zn (II)] or [Mn (II) ] + [Zn (II)] <

: - [HCO3]? [HCO3] - [HC03]

: .-., - -. .. - -. ::

  with [Mn (ll) l, [Zn (ll)] and [Mn (il)] + [Zn (ll)] 0, respectively, o [Mn (ll)], [Zn (ll)] and [HCO3] represent respectively o molar concentrations of Mn (ll), Zn (ll) and HCO3 in the reducing composition and the fixing composition, the application of this composition to the keratin fibers being carried out in the presence

  oxygen, especially oxygen from the air.

  Such a process is particularly simple and rapid. In fact, the use of the catalytic system as defined above in one of the reducing and fixing compositions makes possible during the fixing step a gentle oxidation, without the use of a peroxide oxidizing agent.

  hydrogen and only oxygen from the air.

  This composition can thus be presented in different forms such as foam, gel, thickened lotion which are particularly simple and quick to use. Such gentle oxidation has the advantage of limiting the mechanical degradation of the hair which is usually observed during the fixing step of a conventional process in two stages with a long pause time.

o the oxidizing composition.

  In addition, the pHs of the reducing and catalytic fixing compositions can be chosen close to neutrality, which further reduces the risk of

deterioration of fibers.

  The method of the invention also allows the unwinding of keratin fibers, and in particular of the hair, before the fixing step, and this without any risk of damaging the hair or the crimp. The perm process is thus considerably simplified. -; Another avahtage dion such a process is that it allows to obtain permed hair having a particularly beautiful crimp and

o resistant over time.

  Other characteristics, aspects and advantages of the invention

  will appear even more clearly on reading the detailed description which

  will follow, as well as various concrete examples, but in no way limiting,

intended to illustrate it.

  Although the description which follows essentially revolves around the particular case of hair treatment, it will be noted here that the method according to the invention is applicable to any keratin fiber in general, in particular eyelashes,

whiskers, hair, wool and others.

  The reducing composition eVou ia fixing composition of the process o of the invention contains, in a physiologically acceptable medium, a catalytic system containing at least one salt eVou oxide of Mn (ll) eVou Zn (ll) and at least one alkaline hydrogen carbonate, the proportions of salt eVou oxide of Mn (ll) and / or Zn (ll) and of alkaline hydrogen carbonate being such that: [Mn (II)] <1 with [Mn (II)] 0

[HCO 3]

  [Zn (II)] <1 with [Zn (II)] 0: tHCO3] [Mn (II) + Zn (II)] <1 with [Mn (II)] and [Zn (II)] O o [I \ / ln (ll)], [Zn (ll)] and [HCO31 respectively represent the molar concentrations of Mn (ll), Zn (ll) and HCO3 in the composition

  reducer eVou the composition of flxation.

  o Generally, the tHC ratio) varies from 10-5 to 10- ', preferably

  from 10-3 to 10-2 and is typically of the order of 5.10-3.

  In the case of Znll), the ratio tH (O is generally of the order of

  100 times higher than the ratio in the case of Mnfil) .: - - - -

  Typically, this ratio is 10 or more, preferably 10-3 OR more,

  and preferably of the order of 5.10-.

  In the case of a mixture of Mn (ll) and Zn (ll), the ratio generally varies from 10-5 to 10-4, preferably 10-3 to 10-2, this ratio being chosen

  higher when the proportion of Zn (ll) in the mixture increases.

  Generally, the molar concentration of Mn (l l), Zn (l l) or Mn (ll) + o Zn (ll) in the final composition varies from 10-3 to 10 mM / I, preferably from

-2 to 1mM / I.

  When only one or more salts or oxides of Mn (ll) are used, the molar concentration of Mn (ll) in the final composition is typically of

  -3 to 10- 'mM / I, preferably 10-2 to 10-' mM / I.

  Preferably, when only one or more Zn (II) salts or oxides are used, the Zn (II) concentration in the end composition is 10-2 to 10 mM / I, better still 5.10-4 to 1 mM / I. Among the salts of Mn (ll) and Zn (ll) suitable for the present invention, mention may be made of chloride, fluoride, iodide, sulfate, phosphate, nitrate and

  so perch lorate, salts of ca rboxylic acids and their mixtures.

  By way of example, there may be mentioned manganese chloride, manganese carbonate (for example rhodochrosite), Mn (ll) difluoride, Mn (ll) acetate tetrahydrate, Mn (ll) lactate trihydrate , Mn (ll) phosphate, -. -. Mn (ll) iodide, Mn (ll) nitrate trihydrate, Mnll bromide) and

  s Mn (ll) perchlorate tetrahydrate, and Mn (ll) sulfate monohydrate.

  The particularly preferred salts are the sulfates of Mn and Zn.

  Carboxylic acid salts also include acid salts

  hydroxylated carboxylic acids such as gluconate.

  Among the alkaline hydrogencarbonates, mention may be made of o, hydrogencarbonates of Na, K, and their mixtures, preferably

sodium hydrogen carbonate.

  The vehicle in which the catalyst system of the invention is based is preferably water or an aqueous-alcoholic solution of a polyol or of a lower alcohol such as ethanol, isopropanol, tert-butanol or propylene glycol. The reducing compositions according to the invention contain an effective amount of at least one amino acid comprising at least one thiol group (SH) and preferably only one thiol group, these amino acids possibly being under

  form of salts such as hydrochlorides.

  The preferred amino acids according to the invention are amino acids which contain an amine function in position a with respect to a carboxylic acid function. Preferred amino acids can be represented by the formula: NH2

HS R C COOH

-. - - -

-:

H

  in which R is a divalent, linear or branched hydrocarbon radical, for example C, -C, O, preferably C'-C6, such as a methylene, ethylene, butylene, ethylidene, propylidene radical, a saturated cyclic radical , divalent, optionally substituted, for example C4Ce, a divalent aromatic group, optionally substituted, such as a phenylene radical,

tolylene, xylylene.

  Among the amino acids preferred for the reducing compositions of the invention, mention may be made of cysteine and its derivatives, in particular L-cysteine and L-cysteine hydrochloride and giuthation and its derivatives, in particular

- reduced gluthation .: - -

  In general, the content of amino acid containing a thiol group in the reducing composition is from 0.05 to 10% by weight relative to the total weight of the reducing composition, preferably 0.5 to 5% by weight. Typically, the proportion of amino acid is of the order of 1% by weight relative to the weight

  total of the reducing composition.

  The reducing composition can be in the form of a lotion, thickened or not, a cream, a gel or any other suitable form and can contain additives known for their use in the compositions.

  reducers for permanent hair deformation.

  The reducing composition can also be of the exothermic type, that is to say causing a certain heating during application to the hair, which brings a pleasantness to the person who undergoes the perm or straightening. -: - - -; - - The reductive configuration may possibly contain one or more

  solvents conventionally used in the art.

  o Among these solvents, there may be mentioned alkanols such as for example ethanol, propanol or isopropanol, glycerol, propylene glycol or even diethylene glycol. The maximum solvent concentration is

  generally 20% relative to the total weight of the composition.

  The reducing composition may also contain additives: 5 cosmetics well known for this type of composition such as polymers

  cationic, surfactants, perfumes or even silicones.

  In particular, the reducing composition may preferably contain organic pigments such as melanin. It has been found that the reducing compositions according to the invention promote the incorporation of these

so pigments in fibers.

  According to a first embodiment of the invention, the composition of

  reduction contains the catalytic system of the invention.

  In this case, the pH of the reducing composition generally varies from 3 to 9, preferably from 6 to 9, and better still, varies from 7.5 to 8.5. Obviously, the reducing composition is then preferably free of complexing agent

from Mn eVou Zn, such as EDTA.

  The reducing composition containing the catalytic system of the invention as defined above can then be packaged in different forms, provided however that the catalytic system of the invention contained in the reduction composition is not used.

contact with air oxygen.

  As regards the packaging of the reduction composition, this can be done in different ways: o In a first embodiment, the reducing composition according to the invention can be packaged in the form of an aerosol with a single compartment in which are located the amino acid (s) comprising at least one thiol group, the catalytic system dissolved in a physiologically acceptable medium and a conventional inert propellant gas such as arote, a saturated hydrocarbon such as isopropane or a halogenated hydrocarbon. - In a second embodiment, the reducing composition - according to the invention can be packaged in the form of: a kit comprising two separate containers, one containing the amino acid (s) comprising o at least one thiol group, the other containing the catalytic system of the invention dissolved in a physiologically acceptable medium, the amino acid (s) and the catalytic system being mixed or applied

  successively at the time of employment.

  In a third embodiment, the reducing composition can be contained in a pump system with a single compartment without air intake or in a system with a pump with two compartments, the amino acid (s) comprising at least one thiol group being in a compartment and

  the catalytic system of the invention in the other.

  In a fourth reulisation, the composition according to the invention can be presented in the form of one or more bags impermeable to oxygen. The

  (or the) sachet (s) will advantageously be aluminum sachets.

  If the composition according to the invention is in the form of a single sachet, the latter will contain the amino acid (s) comprising

  minus one thiol group and the catalytic system of the invention.

  If the composition according to the invention is in the form of two sachets, the first sachet will contain the catalytic system of the invention and the second sachet will contain the amino acid (s) comprising at least one thiol group . - - -: s The application of the reducing composition can be carried out before, during or after the usual step of stressing the hair. Preferably, this application is carried out after the power-up step

hair.

  Before proceeding to the next rinsing step, it is conventional to allow the hair to which the composition has been applied to stand for a few minutes, generally between 2 and 40 minutes, preferably between 5 and 20 minutes. reducing, and this so as to give the active ingredients time to act correctly on the hair. This waiting phase is generally carried out by leaving the treated hair to stand in the open air (room temperature), but it can also be carried out at a

higher temperature.

  - During this waiting phase, care is taken that the hair does not dry completely and remains moist until the next stage is implemented (for this purpose, possible use of hats, gels

o protection for example).

  In the second step of the process (step (ii)), the impregnated hair

  of the reducing composition are rinsed thoroughly.

  According to a preferred implementation of the process of the invention, the third step (step (iii)) consists in separating the means (rollers) used for the mechanical tensioning of the keratin fibers from the latter before the application of a oxidizing composition. The keratin fibers, and in particular the hair, are unwound between the

  reduction phase and fixing phase.

  This step of unwinding the hair as well as the next step (step

  o (iv) fixation) present no risk of keratin fibers breaking.

  A direct consequence of this early unwinding compared to a conventional perming process is improved comfort for the client: in fact, the hair remains under tension only during the first stage of the process. The implementation of the rest of the permanent deformation process is also greatly facilitated for the hairdresser as

  can see it in the next step.

  The next step (step (iv)) consists in carrying out on the hair,

  preferably unwound, oxidation.

  - ..:. Although this oxidation step (flxation) can be carried out either by simple contacting of the hair with the oxygen in the air or by application of any fixing composition, and in particular a dilute solution of peroxide hydrogen (generally at a concentration of H2O2 up to 10 volumes), the fixing step will preferably be carried out

  to applying a fixing composition to the keratin fibers.

  The fixing composition which can be used according to the invention may also contain basifying or acidifying agents, preserving agents, opacifiers, thickening agents or even cosmetic additives well known for this type of composition such as stabilizers, cationic polymers, surfactants, viscosity agents, silicones or

perfumes.

  --- This fixing composition can be presented in different forms: shampoo, gel, foam, cream, thickened lotion. Thus, it can be applied very simply, in the same way as a usual care, such as a shampoo or a gel, which is gently lathered by massaging the hair very lightly, then removed by rinsing the fibers

keratin with water.

  A preferred fixing composition is a composition containing the

  catalytic system of the invention as defined above.

  In this case, the pH of the fixing composition generally varies from 3 to 9, preferably from 6 to 9, and better still from 7.5 to 8.5. Obviously, the fixing composition is then preferably free from any Mn eVou Zn complexing agent such as EDTA. -: In addition, the fixing composition will preferably be free of any conventional oxidizing agent such as hydrogen peroxide, alkaline bromates,

  persalts, polythionates and mixtures thereof.

  However, if the oxidation step is carried out using a dilute solution based on hydrogen peroxide, this may for example be stabilized with phenacetin, acetanilide, mono and trisodium phosphates

  s or with 8-hydroxyquinoline sulfate.

  If the fixing composition according to the invention is a preferred fixing composition according to the invention, that is to say a fixing composition comprising the catalytic system of the invention as defined above, this fixing composition may be packaged in different forms,

......

  provided, however, that the catalytic system of the invention contained in the fixing composition is protected from any possible contact with oxygen

air.

  Thus, in a first embodiment, the fixing composition can be packaged in the form of a single compartment aerosol in which there are o the catalytic system dissolved in a physiologically acceptable medium and a conventional inert propellant gas such as nitrogen, a

  saturated hydrocarbon such as isopropane or a halogenated hydrocarbon.

  In a second embodiment, the fixing composition can be

  contained in a single compartment pump system.

  s In a third embodiment, the fixing composition may be in the form of an oxygen-impermeable sachet, preferably a

- aluminum bag. - - - - -

  Finally, the last step (step (v)) of this process is a step

  conventional rinsing of keratin fibers thus treated.

  o We get a nice regular crimp from root to tip, which

  shows good hold even after several shampoos.

  Concrete examples, intended to illustrate the invention without limiting it,

will now be donated.

  In what follows and what precedes, the quantities are expressed in

  percentage by weight relative to the total weight of the compositions.

EXAMPLE 1

  The following reducing and fixing compositions were prepared by simple mixing in the absence of air: - - Compositions Reducing agent Aqueous solution Reducing aqueous solution Ethanol NaHCO3 Mn sulfate Composition R1 500 mg of L hydrochloride - 20 ml solution 1 ml solution 20 ml cvstein in 20 ml of water 1 M 100 mM Composition R2 500 mg of gluthation 20 ml solution 1 ml solution 20 ml reduced in 20 ml of water 1M 100 mM Composition RA 500 mg of hydrochloride 20 ml of L- cysteine in 20 ml of water Composition RB 20 ml solution 20 ml 1M Composition RC 1 ml solution 20 ml mM ComposiDon RD 500 mg hydrochloride of 20 ml solution 20 ml L-cysteine in 20 ml 1 M - water. .. Composition RE 500 mg hydrochloride of - - 1 ml solution 20 ml L- cysteine in 20 ml of water 100 mM Composition RF 500 mg of ascorUic acid in 20 ml solution 1 ml solution 20 ml ml of water 1 M 100 mM The reducing compositions R1 and R2 are compositions according to the invention. The RF composition is a control reducing composition containing a reducing agent (ascorbic acid) outside the present invention. The compositions RA to RE are compositions comprising only some of the constituents of the reducing compositions according to ..

The invention. - - - - -

: -: - - -

  Catalyst oxidizing composition according to the invention 1S Aqueous solution Aqueous solution Ethanol NaHCO3 Mn sulfate Composition 01 20 ml solution 1 ml solution 20 ml 1M 100 mM

EXAMPLE 2

  5 mi of the reducing compounds of Table I Gi- are applied

  s underneath on coiled strands of hair and leave to act for 20 minutes. The locks are rinsed with lukewarm tap water, then the oxidizing compositions of Table I are applied in the open air and left to act for 20

  minutes. The hair is dried and then unwrapped.

o TABLE I

  Test n Reducing composition Oxidizing composition

A RA 01

B RB 01

C RC 01

D RD 01

E RE 01

- F RF 01

1 - - R 1 - - 01

2 R2 01

  The witnesses consist of strands of hair which were

  simply rolled up, rinsed with water, dried and then unwound.

  The locks of hair treated with the process of the invention have a significant and stable permanent deformation, which is greater than that of the control locks and at least equal if not greater than

  that obtained with conventional treatment.

-20 EXAMPLE 3

  5 ml of the reducing compositions of Table II above are applied to locks of curly hair, then the locks are stretched to 100% elongation and left to act with the locks under tension for 20

minutes.

  Rinse, as in Example 1, then apply 5 ml of the oxidizing solution 01 and leave to act for 20 minutes. We dry the hair and then

releases tension.

- :. .

-... -

  s TABLE II | Trial no | Reducing composition | Oxidizing composition |

R2 01

6 R1 01

  The control wick was simply rinsed with energized water and then relaxed. to Solon treated wicks of the invention have an elongation

  permanent compared to the control wick.

  ..: - -.... - ::. -...... -. -: - - - -.

Claims (28)

  1. Process for treating keratin fibers, in particular -. hair, with a view to obtaining permanent deformation of the latter, in particular in the form of permed hair, comprising the following steps: (i) applying to the keratin fibers to be treated a reducing composition, the keratin fibers being tensioned using means (rollers) implemented before, during or after said application; (ii) rinse the keratinous fibers; (i ii) optionally separating the means for tensioning the keratin fibers used in step (i); (iv) fix the keratin fibers; s - either directly by bringing said fibers into contact with the oxygen in the air, -: - - either: by applying to said keratin fibers   - fixing composition; - -: - - -   (v) separating the tensioning means if they were not in step o (iii) and, optionally, (vi) rinsing the keratin fibers again, said process being characterized in that: ( vii) the reducing composition comprises an effective amount of at least one amino acid comprising at least one thiol group, and (viii) at least one of the reducing and fixing compositions comprises, in a physiologically acceptable vehicle, a catalytic system d '' at least one salt and / or oxide of Mn (ll) eVou of Zn (ll), and of at least one hydrogen carbonate of alkali metal, the proportions of salt eVou oxide of Mn (ll) eVou of Zn (ll) and d alkali metal hydrogen carbonate being such that: [Mn (II)] [Zn (II)] or [Mn (II)] + [Zn (II)] < [HCO3] [HC03] [HCO3]   with [Mn (ll)], [Zn (ll)] and [Mn (ll)] + [Zn (ll)] 0, respectively, od [Mn (ll)], [Zn (ll)] and [HCO3] respectively represent the molar concentrations of Mn (ll), Zn (ll) and HCO3 in the reducing composition eVou the fixing composition, the application of this position on the keratin fibers being carried out in the presence of oxygen, in particular oxygen air. 2. Method according to claim 1, characterized in that the ratios [Mn (II)] [Zn (II)] EMn (II)] + [Zn (II)] vary from 10-5 to 10-4, preferably [HC03] [HC03] [HCO3]   -3 to 10-2 and better are around 5.10-3.   3. Method according to any one of the preceding claims,   o characterized in that the salts of Mn (ll) and Zn (ll) are chosen from chloride, fluoride, iodide, sulfate, phosphate, nitrate, perchlorate, the salts   carboxylic acids and mixtures thereof.   4. Method according to claim 3, characterized in that the salt of Mn (ll) and / or Zn (ll) is sulfete.   5. Method according to claim 3, characterized in that the salts   - - carboxylic acids are salts of hydroxylated carboxylic acids.   - - - 6.The method of claim; 5, characterized in that the salt   of hydroxy carboxylic acid is gluconate.   7. Method according to any one of the preceding claims,   o characterized in that the hydrogencarbonate is chosen from sodium hydrogencarbonate, potassium hydrogencarbonate and their mixtures.   8. Method according to any one of the preceding claims   characterized in that the physiologically acceptable vehicle is a hydroalcoholic solution.   9. Method according to any one of the preceding claims,   - characterized in that the amino acid comprising at least one thiol group is chosen from amino acids having an amine function in position a by   with respect to a carboxylic acid function.   n 10. Method according to claim 9, characterized in that the amino acid corresponds to the formula: NH2 HS R C COOH   - - 1: H in which R is a divalent hydrocarbon radical, linear or branched, an optionally substituted divalent saturated cyclic radical or an optionally substituted divalent aromatic group. 11. Method according to claim 10, characterized in that R is a divalent, linear or branched C-CO hydrocarbon radical, preferably in   C'-C6, a saturated cyclic radical divalent to C4-Ce.   12. Method according to any one of claims 1 to 8,   o characterized in that the amino acid is chosen from cysteine and its derivatives, gluthation and its derivatives.   13. Method according to claim 12, characterized in that the acid   amine is chosen from cysteine hydrochloride and gluthation.   - - 14. Method according to claim 13, characterized in that the concentration of amino acid in the reducing composition is from 0.05 to% by weight, preferably from 0.5 to 5% by weight relative to the total weight of composition.   15. Method according to any one of the preceding claims,   characterized in that the reduction composition contains the catalytic system. 16. Method according to claim 15, characterized in that the reduction composition is free from any complexing agent of Mn eVou deZn. 17. Method according to claim 15 or 16 characterized in that the reduction composition has a pH varying from 3 to 9, preferably from 6 to 9, and better from 7.5 to 8.5.   18. Method according to one of the preceding claims 15 to 17,   characterized in that the reduction composition is packaged in the form   an acrosol or a pump system without air intake.   19. Method according to one of claims 15 to 17, characterized in that   that the reduction composition is in the form of two separate components, a first component comprising the catalytic system dissolved in a physiologically acceptable medium, and a second component comprising the compound or compounds comprising at least a thiol group.   20. The method of claim 19, characterized in that the reduction composition is packaged in a pump system with two separate compartments, the compound or compounds comprising at least one thiol group being in one compartment and the catalytic system in the other com pa rti me nt.   21. Method according to one of claims 15 to 17, characterized in that   o that the reduction composition is packaged in the form of one or more   bags impermeable to ox, vgene.   22. Method according to claim 21, characterized in that the reduction composition is packaged in the form of two sachets impermeable to oxygen s - a first sachet comprising the catalytic system, and - a second sachet comprising the compounds comprising - - - - minus one thiol group. - - -:   - - - - - 23. Method according to any of the preceding claims,   characterized in that the step of fixing the keratin fibers is carried out in   o applying a fixing composition to the keratin fibers.   24. Method according to claims 22 or 23 above, characterized   in that the fixing composition contains the catalytic system such as defined in claim 1.   25. The method of claim 24, characterized in that the fixing composition is free of any complexing agent of Mn eVou de Zn. 26. The method of claim 24 or 25, characterized in that the fixing composition has a pH varying from 3 to 9, preferably from 6 to 9, and better from 7.5 to 8.5.   27. Method according to one of claims 24 to 26, characterized in that   that the fixing composition is packaged in the form of an aerosol or a system without return air.   28. Method according to one of claims 24 to 26, characterized in that   that the fixing composition is packaged in the form of a sachet