EP1965867A1

EP1965867A1 - Method for deforming fibres containing keratin

Info

Publication number: EP1965867A1
Application number: EP06818721A
Authority: EP
Inventors: Burkhard Müller; Birgit Rautenberg-Groth
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2005-12-19
Filing date: 2006-11-22
Publication date: 2008-09-10
Also published as: DE102005061021A1; WO2007073809A1

Abstract

The invention relates to a method for the permanent deformation of fibres containing keratin, in particular human hair. According to said method: (i) an aqueous, keratin reducing composition is applied to the fibres in the form of an emulsion containing at least one keratin reducing compound; (ii) the fibres are rinsed after an exposure time Z1 and are optionally dried; (iii) the fibres are then deformed with the aid of auxiliary deformation agents; and (iv) an oxidising composition containing at least one oxidising compound is applied to the fibres and is rinsed off after an exposure time Z2.

Description

"Method for deforming keratin-containing fibers"

The invention relates to a method for permanently deforming keratin-containing fibers, in particular human hair.

As keratin-containing fibers, in principle all animal hair, e.g. Wool, horsehair, angora hair, furs, feathers and products made therefrom or textiles. However, the invention is preferably used as part of a hair shaping, in particular the permanent wavy smoother or smoothing frizzy human hair and wigs made from it.

A permanent deformation keratinhaltiger fibers is usually carried out so as to mechanically deform the fiber and determines the deformation by suitable means. Before and / or after this deformation, the fiber is treated with a keratin-reducing preparation. After a rinsing process, the fiber is then treated in the so-called fixing step with an oxidizing agent preparation, rinsed and freed after or during the fixing step of the shaping aids (winders, papillots). When, as a keratin reducing component, a mercaptan, e.g. Ammonium thioglycolate is used, this part of the disulfide bridges of the keratin molecule cleaves to -SH groups, so that there is a softening of keratin fibers. In the later oxidative fixation again disulfide bridges are knotted in the hair keratin, so that the Keratingefüge is fixed in the predetermined deformation. Alternatively, it is known to use sulfite instead of the mercaptans for hair styling. By bisulfite solutions and / or sulfite solutions and / or disulfite solutions disulfide bridges of keratin in a sulfitolysis according to the equation

R - S - S - R + HSO ₃ ⁽⁾ → R - SH + R - S - SO ₃ ⁰

split and achieved in this way a softening of the keratin fibers. Hydrogen sulfite, sulfite or disulfite containing reducing agents do not have the strong odor of the mercaptan-containing agents. The cleavage can be reversed as described above in a fixing step using an oxidizing agent to form new disulfide bridges.

The permanent smoothing of keratin-containing fibers is achieved analogously by the use of keratin-reducing and -oxidierenden compositions. In a similar process, the frizzy hair is either on a large diameter winder usually wound more than 15 mm or the hair combed smooth under the action of the keratin-reducing composition. Instead of the winder, it is also possible to smooth the fiber on a smoothing board. Smoothing boards are usually rectangular boards, for example made of plastic.

If the permanent deformation of the keratinic fibers is performed so that the fiber is simultaneously exposed to stress and the keratin-reducing composition, there is an increased risk of uneven deformation result and even serious damage to the fiber. This is all the more true in the event that the keratinic fiber is also exposed to elevated temperature at the same time.

EP 083 095 A2 has therefore proposed a method for shaping hair, in which the keratin-reducing preparation is rinsed out before the hair is exposed to elevated temperature. The mechanical deformation may be carried out before applying the keratin-reducing preparation, after applying the keratin-reducing preparation and before rinsing out this preparation or after applying the keratin-reducing preparation and after rinsing out this preparation. It is not described that it may be detrimental when the hair is exposed to the keratin reducing composition while under tension. Commercially available corrugating agents are used as the keratin-reducing preparation. On special properties of these means is not turned off.

From US 2,405,166 a method for permanent waves of hair is known, which is characterized in that the keratin-reducing preparation is rinsed out before the mechanical deformation and further treatment steps. This avoids too much curling and damage to the hair. As a keratin-reducing preparation simply composed aqueous solutions are used. A disadvantage of the use of such solutions is that they adhere poorly to the hair and therefore run lightly or even drip off the treated hair. This can lead to unnecessary contact of the scalp with the reducing agent or an uneven reduction of the fibers.

The object of the invention is therefore to provide a deformation process for keratin fibers, especially for human hair, which provides a uniform deformation result, prevents excessive damage to the fibers and also ensures that the scalp is not unnecessarily burdened.

Surprisingly, it has been found that the object is achieved by a method in which the keratin-containing fibers, in particular human hair, first treated with a reducing agent preparation, then rinsed and only after the Reducing agent preparation was rinsed out, be deformed with the aid of deformation aids, wherein the reducing agent preparation is present as an emulsion.

A first subject of the invention is therefore a process for permanently deforming keratin-containing fibers, in particular human hair, wherein

(i) an aqueous, keratin-reducing composition containing at least one keratin-reducing compound to which fibers are applied, (ii) the fibers are rinsed after a contact time Z1 and optionally dried, (iii) the fibers are subsequently deformed with the aid of deformation aids and ( iv) finally an oxidizing composition containing at least one oxidizing compound is applied to the fibers and rinsed off again after a contact time Z2,

and wherein the aqueous, keratin-reducing composition is in the form of an emulsion.

The inventive method is characterized in particular by a special uniformity of the deformation, and a low load of fiber and scalp.

Deformation aids in the sense of the method according to the invention can e.g. Curlers or papillotes in the case of a perm, or aids for a mechanical smoothing, such as a comb or a brush, a smoothing board or a heatable smoothing iron in case of hair straightening. When the forming aids, such as winder, are attached to the fiber by a permanent wave process for a prolonged period of time, it may be desirable to remove these deformation aids before, during or after step (iv). It may be advantageous in this connection to leave the deformation aids in the hair during step (iv), then to remove them and thereafter repeat step (iv) as so-called postfixing step (v).

An aqueous composition according to the invention contains at least 50% by weight of water, based on the weight of the total composition.

A crucial step of the process according to the invention is the rinsing out of the reducing agent preparation before the mechanical deformation of the fibers. This ensures that a uniform deformation result is achieved. It is also essential that the aqueous, keratin-reducing composition is present as an emulsion. Surprisingly It has been shown that the emulsion remains evenly distributed in the hair during the exposure time Z1 and does not run or drip off the fiber.

The aqueous, keratin-reducing composition preferably has a viscosity of 1000

50000 mPa-s, in particular of 5,000-20,000 mPa.s at 2O ⁰ C (measured with a Brookfield viscometer, spindle no. 6 rpm at 20). In this case, the viscosity can be adjusted solely by selecting the type and amount of immiscible liquids that form the emulsion.

Preferably, however, the aqueous, keratin-reducing composition for adjusting the viscosity additionally contains at least one viscosity-increasing compound, hereinafter referred to as thickener.

Thickeners which can be used according to the invention are, for example, agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, and viscosity-increasing polyacrylate-based polymers such as those sold under the trade names Pemulen ^® , Aculyn ^® and Carbopol ^® . Furthermore, preference is given to using a mixture of diesters of 1,2-propylene glycol with fatty acids, for example the thickener having the INCI name Propylene Glycol Dicaprylate / Dicaprate.

The aqueous keratin-reducing composition particularly preferably contains a hydroxyalkylcellulose as thickener. Suitable hydroxyalkylcelluloses are commercially available and are sold for example under the trade names Natrosol ^® (company Hercules), Cellosize ^® (Amerchol) and Tylose ^® (Clariant). Are very particularly preferably hydroxyethyl, in particular the hydroxyethyl cellulose from Hercules under the name Natrosol ^® 250 HR marketed.

The aqueous, keratin-reducing composition contains the thickener preferably in an amount of 0.05 to 20 wt .-%, particularly preferably from 0.1 to 10% by weight and very particularly preferably from 0.1 to 5 wt .-%, in each case based on the total aqueous, keratin-reducing composition.

The aqueous keratin-reducing composition may be in the form of an oil-in-water (O / W) emulsion, a water-in-oil (W / O) emulsion or a multiple emulsion. Preferably, the aqueous keratin reducing composition is in the form of an oil-in-water emulsion. Emulsions are generally understood to mean heterogeneous systems which consist of two liquids that are immiscible or only slightly miscible with one another, which are usually referred to as phases. In an emulsion, one of the liquids is dispersed in the form of fine droplets in the other liquid under the expense of energy to create stabilizing phase interfaces. Emulsions are known in which a permanent dispersion of a liquid in another liquid can be achieved without the addition of further auxiliaries. In general, however, it is advisable to stabilize emulsions by adding so-called emulsifiers.

The aqueous, keratin-reducing composition therefore preferably contains at least one emulsifier. Emulsifiers effect at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Further definitions and properties of emulsifiers can be found in "H. -D. Dörfler, Grenzflächen- and Kolloidchemie, VCH Verlagsgesellschaft mbH., Weinheim, 1994". Emulsifiers which can be used according to the invention are, for example

Addition products of 4 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of from 1 to 30 moles of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol, ethylene oxide and polyglycerol addition products of methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, with degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as sugar component being preferred,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example, the commercially available product ^® Montanov 68,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Partial esters of polyols of 3-6 carbon atoms with saturated fatty acids of 8 to 22

C-atoms,

Sterols. Sterols are understood to mean a group of steroids which bind to C-atom 3 of the

Steroid scaffold carry a hydroxyl group and both from animal tissue

(Zoosterine) as well as vegetable fats (phytosterols) are isolated. examples for Zoosterins are cholesterol and lanosterol. Examples of suitable phytosterols are

Ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

Phospholipids. Of these, especially the glucose phospholipids, e.g. as lecithins or phosphatidylcholines from e.g. Egg yolk or plant seeds (e.g., soybeans) are understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

Polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate

(Dehymuls ^® PGPH commercial product), linear and branched fatty acids having 8 to 30 C - atoms and their Na, K, ammonium,

Ca, Mg and Zn salts.

The emulsifiers are preferably used in amounts of 0.1 to 25 wt .-%, in particular 0.1 to 3 wt .-%, based on the respective total composition.

Preference is given to nonionic emulsifiers having an HLB value of 8 to 18, according to the methods described in the Römpp Lexikon Chemie (Hrg. J. Falbe, M. Regitz), 10th edition, Georg Thieme Verlag Stuttgart, New York, (1997), page 1764, listed definitions. Nonionic emulsifiers with an HLB value of 12 to 18 are particularly preferred according to the invention. Very particular preference is given to polyethylene glycol monolauryl ether with about 23 molar equivalent of ethylene oxide (INCI name: Laureth-23). This has an HLB value of 16.9.

The emulsion-form, aqueous, keratin-reducing composition contains water as one of the at least two immiscible or poorly miscible liquids. The second liquid is preferably an oil, both natural and synthetic oils, such as vegetable oils, liquid paraffin oils, but also ester oils, dicarboxylic acid esters, symmetric, unsymmetrical or cyclic esters of carbonic acid with fatty alcohols, triflic acid esters of fatty acids with glycerol, fatty acid partial glycerides and fatty alcohols are suitable.

Preferably, aqueous, keratin-reducing compositions are used which contain as second liquid at least one linear or branched, saturated or unsaturated fatty alcohol. Fatty alcohols which may be used are fatty alcohols with C ₆ -C ₃₀ -, preferably C ₁₀ -C ₂₂ - and very particularly preferably C ₁₂ -C ₂₂ - groups. For the purposes of the invention, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucalcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, as well as their Guerbet alcohols, these lists have exemplary and not limiting character should. However, the fatty alcohols are derived from preferably natural fatty acids, which usually can be assumed by recovery from the esters of fatty acids by reduction. Also usable according to the invention are those fatty alcohol cuts which are produced by reduction of naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols. Such substances are, for example, under the names Stenol ^® such as Stenol ^® 1618 or Lanette ^® such as Lanette ^® O or Lorol ^®, for example, Lorol ^® C8, Lorol C14 ^®, Lorol C18 ^®, ^® Lorol C8-18, HD Ocenol ^®, Crodacol ^® such as Crodacol ^® CS, Novol ^®, Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or Isocarb® ^® 24 available for purchase. Of course, the invention also wool wax alcohols, as are commercially available, for example under the names of Corona ^®, White Swan ^®, Coronet ^® or Fluilan ^® can be used. Particularly preferred mixtures of stearyl alcohol and cetyl alcohol are used, which are referred to in the INCI nomenclature as Cetearyl Alcohol.

The fatty alcohols are used, for example, in amounts of from 0.1 to 20% by weight, based on the total preparation, preferably in amounts of from 0.1 to 10% by weight.

The reaction time Z1 is preferably 5-60 minutes, more preferably 10-30 minutes. The reaction time Z2 is preferably 1-30 minutes, more preferably 5-20 minutes.

The keratin-reducing compounds contained in the aqueous composition of step (i) are preferably selected from compounds having at least one thiol group and derivatives thereof, sulfites, hydrogen sulfites and disulfites.

Compounds having at least one thiol group and derivatives thereof include, for example, thioglycolic acid, thiolactic acid, thiomalic acid, phenylthioglycolic acid, mercaptoethanesulfonic acid and its salts and esters (such as isooctylthioglycolate and isopropylthioglycolate), cysteamine, cysteine, Bunte salts and salts of sulfurous acid. Preferably suitable are the Monoethanolammoniumsalze- or ammonium salts of thioglycolic acid and / or thiolactic acid and the free acids. These are preferably used in the aqueous composition in concentrations of from 0.5 to 2.0 mol / kg at a pH of from 5 to 12, in particular from 7 to 9.5. To adjust this pH, the aqueous compositions usually contain alkalizing agents such as ammonia, alkali metal and ammonium carbonates and bicarbonates or organic amines such as monoethanolamine. Examples of keratin-reducing compounds of the disulfites which may be contained in the aqueous composition are alkali disulfites such as sodium disulfite (Na ₂ S ₂ O ₅ ) and potassium disulfite (K ₂ S ₂ O ₅ ), and magnesium disulfite and ammonium disulfite ((NH ₄ J ₂ S ₂ O ₅ ) According to the invention, ammonium bisulfite may be preferred Examples of keratin-reducing compounds of hydrogen sulfites which may be present in the aqueous composition are hydrogen sulfites as alkali, magnesium, ammonium or alkanolammonium salt based on a C ₂ -C ₄ mono-, di- or trialkanolamine. ammonium bisulfite can be a particularly preferred hydrogen sulfite. Examples of keratin-reducing compounds of sulfites, which may be included in the aqueous composition, sulfites as alkali metal, ammonium or alkanolammonium salt Base of a C ₂ -C ₄ -mono-, di- or trialkanolamine Ammonium sulfite is preferred here The pH of the w When using sulfite and / or disulfite and / or hydrogen sulfide, the aqueous composition is preferably adjusted to a value in the neutral range from pH 5 to 8, preferably from pH 6 to 7.5.

Preferred C ₂ -C ₄ -alkanolamines according to the invention are 2-aminoethanol (monoethanolamine) and N, N, N-tris (2-hydroxyethyl) amine (triethanolamine). Monoethanolamine is a particularly preferred C ₂ -C ₄ alkanolamine, which is used in particular in an amount of 0.2 to 6 wt .-% based on the total aqueous composition.

The keratin-reducing compounds contained in the aqueous composition of step (i) are particularly preferably selected from thioglycolic acid, thiolactic acid and cysteine and salts thereof.

The keratin-reducing compound is preferably used in an amount of 1 to 25 wt .-%, particularly preferably in an amount of 5 to 15 wt .-%, based on the total aqueous keratin-reducing composition.

In addition, the aqueous keratin-reducing composition may contain other components that promote the action of the keratin-reducing compound on the keratin. Such components include swelling agents for keratin fibers such as CrC ₆ alcohols and water-soluble glycols or polyols such as glycerol, 1, 2-propylene glycol or sorbitol and urea or urea derivatives such as allantoin and guanidine and imidazole and its derivatives. In a preferred embodiment, the aqueous composition contains 0.05 to 5 wt .-% 1, 2-propylene glycol and / or 0.05 to 5 wt .-% urea. The amounts are based on the total aqueous composition.

A dry keratin-containing fiber according to step (ii) of the method according to the invention is present when the water residues adhering to the hair have evaporated to such an extent that the hairs fall individually. Preferably, in a dry keratin fiber, either of Moisture content of the fiber with the humidity of the air is substantially in equilibrium or the fiber absorbs moisture from the air of the environment.

In step (iv) of the method according to the invention, the deformed keratinic fibers are fixed by applying an oxidizing composition. The oxidizing compound contained in the oxidizing composition has such a redox potential that two mercapto groups can be oxidized to form a disulfide bridge. A preferred oxidizing agent is selected from, for example, sodium bromate, potassium bromate or hydrogen peroxide. It is particularly preferable to use hydrogen peroxide as the oxidizing agent. To stabilize aqueous hydrogen peroxide preparations, customary stabilizers can additionally be added. The pH of the aqueous H ₂ O ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H ₂ O ₂ , is preferably from 2 to 6. Concentrates of usually up to 30% may also be used Wt .-% H ₂ O ₂ are used, which are diluted before use. In this case, it may also be preferred to use commercial fast fixings, for example Henkel Natural Styling Rinse Neutraliser 1: 4. If the agent according to the invention contains bromate as the oxidizing agent, this is usually contained in concentrations of 1 to 10% by weight and the pH of the solutions is adjusted to 4 to 7.

Both the aqueous keratin-reducing composition and the oxidizing composition may further contain all other ingredients conventional for such compositions. Such ingredients can be, for example, conditioning agents, surfactants, UV stabilizers, preservatives, complexing agents, thickeners or viscosity-increasing additives.

The conditioning agents used are preferably ammonium salts, particularly preferably trimethylhexadecylammonium chloride, which is referred to in the INCI nomenclature as Cetrimonium Chloride, and / or the poly (dimethyldiallylammonium chloride) known under the INCI name Polyquaternium-6.

Suitable surfactants are all surfactants from the group of nonionic, anionic, and amphoteric surfactants, the group of amphoteric or ampholytic surfactants comprising zwitterionic surfactants and ampholytes. The surfactants have, inter alia, the task of promoting the wetting of the keratin surface by the treatment solution. The surfactants may also have emulsifying effect.

Suitable anionic surfactants are in principle all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or Phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, linear and branched fatty acids having 8 to 30 C atoms (Soap),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear

Is an alkyl group having 8 to 30 carbon atoms and x is 0 or 1 to 16,

Acylsarcosides having 8 to 24 C atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 C atoms in the acyl group,

Sulfobernsteinsäuremono- and -dialkylester having 8 to 24 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefinsulfonates with 8 to 24 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-

A-37 23,354,

Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols containing adducts of about 2-

15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E1-I),

R ¹ (OCH ₂ CH ₂ ) _n -O-p -OR ² (E1-I)

I

OX

in the R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another for hydrogen or a C1 to C4 -

Hydrocarbon radical, is, sulfated fatty acid alkylene glycol esters of the formula (E1-II)

R ⁷ CO (AIkO) _n SO ₃ M (E1-II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or

CH ₂ CHCH ₃ , n is from 0.5 to 5 and M is a cation, as described in DE-OS 197

36,906 are described

Monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _x - COR ⁸

CHO (CH ₂ CH ₂ O) _x H

I CH ₂ O (CH ₂ CH ₂ O) ₂ -SO ₃ X

in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for O or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Preferably, monoglyceride sulfates of the formula (E1-III) are used in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms, as described, for example, in EP 0 561 825 B1, EP 0 561 999 B1, DE 42 04 700 A1 or AKBiswas et al. in J.Am.Oil. Chem. Soc. 37, 171 (1960) and FUAhmed in J.Am.Oil.Chem.Soc. 67, 8 (1990), amide ether carboxylic acids as described in EP 0 690 044, condensation products of C ₈ -C ₃₀ fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the person skilled in the art as protein fatty acid condensates, such as for example, the Lamepon® ^® - types Gluadin® ^® - types Hostapon® ^® KCG or Amisoft ^® - types.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and Eiweissfettsäurekondensate. Zwitterionic surfactants are surface-active compounds which have in the molecule at least one quaternary ammonium group and at least one -COO * ^" '- or -SO _3'. ^'' Group carry Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl N, N-dimethylammonium glycinates, for example cocoalkyldimethylammoniumglycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, in each case with A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name cocamidopropyl betaine.

Ampholytes are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C atoms in the alkyl group. Particularly preferred ampholytes are N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate and C ₂ - C ₁₈ - sarcosine.

Nonionic surfactants contain as hydrophilic group e.g. a polyol group, one

Polyalkylene glycol ether group or a combination of polyol and Polyglykolethergruppe.

Such compounds are, for example

Addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, which are optionally substituted with at least one further hydroxy group, to fatty acids having 8 to 30 carbon atoms and to alkylphenols with 8 to 15 carbon atoms in the alkyl group, with a methyl or C ₂ -C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 C atoms, onto fatty acids having 8 to 30 carbon atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the types, Ci ₂ -C ₃₀ available under the trade names Dehydol ^® LS, Dehydol ^® LT (Cognis) - Fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),

- alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of the formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I)

in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is} linear or branched alkyl radicals having 1 to 4 carbon atoms and w is a number from 1 to 20 stands, amine oxides,

Hydroxymix ethers, as described for example in DE-OS 19738866, sorbitan fatty acid esters and addition products of ethylene oxide to sorbitan fatty acid esters such as the polysorbates, sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide to fatty acid alkanolamides and fatty amines, sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

R ⁴ O- [GJ _p (E4-II)

in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature is here on the review by Biermann et al. in Starch / Stärke 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW Journal Heft 8, 598 (1995).

The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in the individual molecule must always be integer and here before For all given values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and the like technical mixtures, as obtained for example in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxo synthesis. Preference is given to alkyl oligoglucosides of chain length C ₈ -C ₀ (DP = 1 to 3), which are obtained as first runnings in the separation of technical C ₈ -C ₁₈ alcohol -Kokosfett- and with a proportion of less than 6 wt .-% C ₁₂ alcohol can be contaminated and alkyl oligoglucosides based on technical Cg _/ n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated Ci _2/14 coconut alcohol with a DP of 1 to 3. Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamides, a nonionic Ten sid of formula (E4-III),

R ⁶ R ⁵ CO-N- [Z] (E4-III)

R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, and International Patent Application WO 92/06984. An overview of this topic by H.Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988). The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):

R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ CH ₂ OH (E4-I V)

Preferably used as fatty acid N-alkylpolyhydroxyalkylamide glucamides of the formula (E4-IV), in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO for the Acyl of caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petro-, linoleic, linolenic, gadoleic, behenic or erucic acid or those technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

As preferred nonionic surfactants, amine oxides and the alkylene oxide addition products have proved to be saturated linear fatty alcohols, which are optionally substituted by at least one further hydroxy group, and fatty acids containing from 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

Particularly preferred nonionic surfactants are N, N-cocoalkylamine N.Dimethyl-N-oxide with the INCI name Cocamine Oxide, which is for example marketed under the name Aromox ^® by the company Akzo Nobel, as well as the alkoxylated lauryl glycol ether with the INCI name PPG-1-PEG-9 lauryl glycol ether, which is marketed for example under the name Eumulgin ^® L by the company Cognis.

Furthermore, the sugar surfactants may be present as nonionic surfactants. These are preferably present in amounts of 0.1 to 20 wt .-%, based on the respective total composition. Amounts of 0.5 to 15 wt .-% are particularly preferred, and very particularly preferred amounts of from 0.5 to 7.5 wt.%.

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to use native plant or animal raw materials in the manufacture of these substances, so that one can Substance mixtures with different, depending on the particular raw material alkyl chain lengths obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

The surfactants are used in amounts of from 0.1 to 45% by weight, preferably 0.5 to 30% by weight and very particularly preferably from 0.5 to 25% by weight, based on the particular total composition used according to the invention.

The preservatives used are preferably parabens, particularly preferably methylparaben.

Preferred complexing agents are EDTA, NTA, organophosphonic acids, dipicolinic acid, salicylic acid, more preferably 1-hydroxyethane-1, 1-diphosphonic acid.

Furthermore, the aqueous, keratin-reducing composition and / or the oxidizing composition may contain all customary further auxiliaries and additives. For example, the following compounds may be included:

• linear and / or branched fatty acids, preferably C ₂ -C ₃ o-fatty acids, particularly preferably C ₄ -C ₈ fatty acids, most preferably C ₆ -C ₁₀ fatty acids and / or their physiologically acceptable salts; other examples are formic, acetic, propionic, butyric, isobutyric, valeric, isovaleric, pivalic, oxalic, malonic, succinic, glutaric, lactic, glyceric, glyoxylic, adipic, pimelic, suberic, azelaic, sebacic, propiolic, crotonic, isocrotonic, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, Toluoylsäure, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminsäure, 4,4 ^{^{'-Dicyano-6,6'}} -binicotinic acid, 8-carbamoyloctanoic acid, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6,7-naphthalenepentaacetic acid, Malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid,

• polyhydroxy compounds; These are to be mentioned in particular

- Sugars with 5 and / or 6 carbon atoms, especially as mono- and / or oligosaccharides, for example glucose, fructose, galactose, lactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose and / or their derivatives, eg Ether derivatives, amino derivatives and / or acetyl derivatives such as acetylated glucose, e.g. Tetraacetylglucose, pentaacetylglucose and / or 2-acetamido-2-deoxyglucose. Preferred sugar building blocks are glucose, fructose, galactose, allose, lactose, arabinose and sucrose; Glucose, galactose and lactose are particularly preferred;

- Onic acids, in particular gluconic acid, glucuronic acid;

Polyols, e.g. Glucamines, glycerol, mono- or diglycerides, 2-ethyl-1,3-hexanediol, 2-hydroxymethylpropanetriol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol;

Polyhydroxy acids, e.g. Pentahydroxyhexanoic acid, tetrahydroxypentanoic acid and / or derivatives thereof, e.g. Ethers, esters and / or amides, e.g. Pentahydroxyhexansäureamid and / or their physiologically acceptable salts; _further examples: citric acid, malic acid or tartaric acid;

• pantolactone;

• panthenol and / or its derivatives;

• other vitamins, e.g. Vitamin B6, C and / or E and / or their derivatives;

Hydroxy acids, e.g. α-, ß-hydroxy fatty acids or keto fatty acids and / or their physiologically acceptable salts; such as salicylic acid or lactic acid, glyoxylic acid, glycolic acid.

• water-soluble polymers firming action, e.g. Polyvinyl pyrrolidone, vinyl acetate / crotonic acid copolymers,

Antidandruff agents such as e.g. Picrotone Olamine, Zinc Omadine,

• active ingredients such as allantoin, pyrrolidonecarboxylic acids, plant extracts,

PH adjusting and buffering agents, e.g. Citric acid / sodium citrate, ammonium carbonate, ammonium bicarbonate, guanidine carbonate, ammonia, sodium hydroxide, phosphoric acid,

• light stabilizer (UV absorber),

Oil, fat and wax components, preferably in emulsified form,

Dyes, opacifiers and pearlescing agents,

• perfume as well

• optionally aerosol propellants. In a preferred embodiment of the invention, the keratin-containing fibers are moistened prior to step (i). This can be done by spraying the fibers with a liquid, preferably water. Preferably, prior to step (i), the fibers are shampooed with a conventional shampoo, rinsed and then toweled with a towel. After completion of the terry step remains a noticeable residual moisture in the hair back.

In a further preferred embodiment of the invention, the keratinic fibers are subjected to a temperature treatment. It has proved to be particularly advantageous to carry out the temperature treatment only after rinsing out the aqueous, keratin-reducing composition. In this procedure, the keratin fiber to be deformed is not simultaneously exposed to the reducing agent and thermal stress. An over-treatment, i. Too much deformation, and a strong damage to the fibers can be avoided.

Preferably, therefore, the keratinic fibers are heated between the treatment steps (ii) and (iii), during the treatment step (iii) and / or after the treatment step (iii), wherein the heating after the treatment step (iii), i. after the mechanical deformation of the keratinic fibers, is particularly preferred.

The temperature treatment can be carried out, for example, by means of heatable winders, the supply of heated air, for example by means of a hair dryer or dryer hood or in the event that the keratinic fibers are to be smoothed, with the aid of appropriately tempered plates, in particular metal or ceramic plates.

In the temperature treatment, the keratinic fibers are preferably heated to a temperature of 5O ⁰ C to 220 ° C. If the deformation is a corrugation, a temperature range from 5O ⁰ C to 15O ⁰ C _1, in particular from 8O ⁰ C to 14O ⁰ C, is preferred. If it is in the deformation of a smoothing, higher temperatures, for example 12O ⁰ C to 220 ° C, more preferably 13O ⁰ C to 200 ⁰ C, preferably.

Following the implementation of the method according to the invention, the keratinic fibers can be aftertreated in the usual way. For example, the use of a commercial conditioner may be advantageous. A treatment with a conditioner can also be carried out between step (iii) and (iv) of the method according to the invention.

The invention will be further elucidated with reference to the following examples, which examples are intended to facilitate the understanding of the principle of the invention and should not be taken as limiting. Examples:

It became a reforming agent, i. an aqueous, keratin-reducing composition prepared according to Table 1 in the form of an O / W emulsion. Furthermore, two fixatives, i. oxidizing compositions, provided according to Table 2.

Table 1: Forming agent

Mixture of 50 wt .-% cetyl and 50 wt .-% stearyl alcohol

Fatty alcohol sulfate sodium salt (about 90-96% active ingredient content, INCI name: Sodium Cetearyl Sulfate) (Cognis)

Polyethylene glycol monolauryl ether, dodecanol with approx. 23 molar equivalent of ethylene oxide (INCI name: Laureth-23) (Uniquema) Hydroxyethylcellulose (Hercules)

1-Hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Table 2: Fixative

Lauryl glycol ether, ethoxylated with 1 unit of propylene oxide and 9 units of ethylene oxide (INCI).

Name: PPG-1-PEG-9 Lauryl glycol ether) (Cognis)

N, N-dimethyl-N-cocoalkylamine-N-oxide (about 30% active ingredient; INCI name:

Cocamine Oxide) (Akzo Nobel)

Trimethylhexadecylammonium chloride (about 24-26% active ingredient; INCI name: Aqua

(Water), Cetrimonium Chloride (Cognis)

Poly (dimethyldiallylammonium chloride) (about 40% solids, INCI name:

Polyquaternium-6) (Ondeo Nalco)

10 hydrogenated castor oil with approx. 40-45 EO units (INCI name: PEG-40 Hydrogenated

Castor OiI) (BASF)

Experimental procedure and evaluation of the results:

Undamaged hair was moistened with water and toweled with a towel.

The reshaping agent was uniformly applied to the entire hair. After a period of exposure of 20 minutes, the hair was rinsed, gently toweled with a towel and wound on winder with a diameter of 8 millimeters. The winders were heated to about 12O ⁰ C. After about 10 minutes, the heat was stopped. Once the hair had cooled to room temperature, it was treated with one of the fixatives shown in Table 1. After 15 minutes exposure time, the wipers were removed, the hair rinsed with water and finally dried. This procedure was run through with both fixers F1 to F2. Regardless of the fixative used, a very uniform wave result was achieved with little hair damage.

Claims

Patent claim:

1. A method for permanently deforming keratin-containing fibers, in particular human hair, wherein

(I) an aqueous, keratin-reducing composition containing at least one keratin-reducing compound is applied to the fibers, (ii) the fibers are rinsed after a contact time Z1 and optionally dried, (iii) the fibers are subsequently deformed with the aid of deformation aids and (iv ) Finally, an oxidizing composition containing at least one oxidizing compound is applied to the fibers and rinsed again after a contact time Z2,

characterized in that the aqueous, keratin-reducing composition is present as an emulsion.

2. The method according to claim 1, characterized in that the aqueous, keratin-reducing

Composition has a viscosity of 1000 to 50,000 mPa-s, measured at 2O ⁰ C with a Brookfield viscometer having.

3. The method according to any one of claims 1 or 2, characterized in that the aqueous keratin-reducing composition is present as an emulsion of the oil-in-water type.

4. The method according to any one of claims 1 to 3, characterized in that the aqueous keratin-reducing composition contains 0.1 to 25 wt .-%, based on the total composition, of at least one ionic or nonionic emulsifier.

5. The method according to any one of claims 1 to 4, characterized in that the aqueous keratin-reducing composition contains at least one nonionic emulsifier having an HLB value of 8 to 18.

6. The method according to any one of claims 1 to 5, characterized in that the aqueous keratin-reducing composition contains at least one thickener.

7. The method according to claim 6, characterized in that the aqueous keratin-reducing composition contains as thickening agent a hydroxyalkylcellulose.

8. The method according to any one of claims 1 to 7, characterized in that the keratin-reducing compound is selected from thioglycolic acid, thiolactic acid, thiomalic acid, phenylthioglycolic acid, mercaptoethanesulfonic acid and their salts and esters, cysteamine, cysteine, Bunte salts and salts of sulfurous acid, Alkalidisulfiten , such as sodium disulfite (Na ₂ S ₂ O ₅ ) and potassium bisulfite (K ₂ S ₂ O ₅ ), as well as magnesium disulfite and ammonium disulfite ((NH ₄ J ₂ S ₂ O ₅ ), hydrogen sulfites as alkali, magnesium, ammonium or Alkanolammonium salts based on a C ₂ -C ₄ -MOnO-, di- or trialkanolamine, and sulfites as alkali, ammonium or alkanolammonium salts based on a C ₂ -C ₄ mono-, di- or trialkanolamine.

9. The method according to claim 8, characterized in that the keratin-reducing compound is selected from thioglycolic acid, thiolactic acid and cysteine and salts thereof.

10. The method according to any one of claims 1 to 9, characterized in that the keratin-reducing compounds in an amount of 1-25 wt .-%, based on the total aqueous keratin-reducing composition are included.

11. The method according to any one of claims 1 to 10, characterized in that the oxidizing composition used in step (iv) contains as the oxidizing compound hydrogen peroxide.

12. The method according to claim 11, characterized in that the oxidizing composition contains hydrogen peroxide in an amount of 0.5 to 3.0 wt .-%, based on the total oxidizing composition.

13. The method according to any one of claims 1 to 12, characterized in that the keratin-containing fibers before step (i) are moistened.

14. The method according to any one of claims 1 to 13, characterized in that the keratinic fibers between the treatment steps (ii) and (iii), during the treatment step (iii) and / or after the treatment step (iii) are heated.

15. The method according to claim 14, characterized in that the keratinic fibers after the treatment step (iii) are heated.

16. The method according to any one of claims 14 to 15, characterized in that the keratinic fibers are heated to a temperature of 5O ⁰ C to 22O ⁰ C.