EP1463484A1

EP1463484A1 - Method for the permanent deformation of keratin fibres, and agent

Info

Publication number: EP1463484A1
Application number: EP02796590A
Authority: EP
Inventors: Detlef Fischer; Swenja Kalischke; Burkhard Müller
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-12-18
Filing date: 2002-12-09
Publication date: 2004-10-06
Also published as: WO2003051320A1; DE10162143A1; AU2002361993A1

Abstract

The invention relates to a method for the permanent deformation of keratin fibres. According to the inventive method, the fibre is treated with an aqueous preparation (A) of a keratin-reducing substance before and/or after a mechanical deformation. After an exposure time, said fibre is rinsed with water and/or an aqueous agent, and an aqueous preparation (B) is applied. After an exposure time, the fibre is fixed by means of an aqueous preparation (C) of an oxidant, is optionally rinsed after an exposure time, and is optionally post-treated. Said preparation (B) contains at least one protein hydrolysate and at least one amino acid.

Description

Process for permanent deformation of keratin fibers and agents

The invention relates to a process for the permanent deformation of keratin fibers, in particular human hair, by reductive splitting and renewed oxidative formation of disulfide bonds in keratin, and the use of agents suitable for this process.

The permanent deformation of keratin fibers is usually carried out in such a way that the fiber is mechanically deformed and the deformation is determined by suitable aids. Before and / or after this deformation, the fiber is treated with the aqueous preparation of a keratin-reducing substance and rinsed with water or an aqueous solution after an exposure time. In a second step, the fiber is then treated with the aqueous preparation of an oxidizing agent. After an exposure time, this is also rinsed out and the fiber is freed from the mechanical deformation aids (curlers, papillots).

The aqueous preparation of the keratin reducing agent is usually made alkaline, so that on the one hand a sufficient proportion of the thiol functions are deprotonated and on the other hand the fiber swells and in this way a deep penetration of the keratin-reducing substance into the fiber is made possible. The keratin-reducing substance cleaves a part of the disulfide bonds of the keratin to -SH groups, so that the peptide cross-linking is loosened and the fiber deformation due to the mechanical deformation leads to a reorientation of the keratin structure. Under the influence of the oxidizing agent, disulfide bonds are again formed, and in this way the keratin structure is re-fixed in the predetermined deformation. A known method of this type is permanent wave treatment of human hair. This can be used both for producing curls and waves in straight hair and for straightening curly hair. However, a negative side effect of the permanent waving of the hair that is carried out in this way is often embrittlement and dulling of the hair. Furthermore, in many cases, other properties such as wet and dry combability, grip, smoothness, softness, gloss and tear resistance are also influenced in an undesirable manner.

Among other things, these negative side effects are influenced by the condition of the parent hair and essentially by the pH of the reducing solution. A low pH generally leads to fewer undesirable effects, but the wave power and the durability of the perm are often not sufficient. On the other hand, a higher pH value leads to a satisfactory wave output, but also to significantly increased negative side effects, especially on hair that has already been preloaded. An optimally formulated permanent waving agent should therefore specifically enable a desired shaping performance while influencing the hair structure as little as possible.

Nourishing additives and film formers are often added to the permanent waving agent without, however, significantly improving the hair structure. For this purpose, high-molecular polymers are used, for example, which attach to the top layer of skin and hair and there produce an external, subjectively perceptibly improved handle on the hair. The structural damage to the inside of the hair, which is caused by the reduction process in the case of perms, cannot be reduced, however, because the substances cannot penetrate the hair due to their size.

EP 723 772 describes that alkalizing agents such as basic amino acids together with cationic polymers in the waving agent cause the hair to swell more. On the one hand it leads to stronger shaping and longer durability of the perm, but on the other hand it also leads to the observed hair damage. In the published patent application GB 216041 9, a method is described in which hair, skin or nails ^■ first be treated with a reducing agent, which is then rinsed. Then an aqueous protein hydrolyzate, preferably with a molecular weight greater than 50,000 Daltons, is applied to the areas to be treated, after which the neutralization is carried out. Subjectively, the area treated in this way felt better, hair damage was reduced on the inside, however (due to the high

Molecular weight) not.

The object of the invention is to find a process for the permanent deformation of keratin fibers, in which not only the surface of the hair is improved, but also the damage inside the fibers is reduced, and in which the further undesirable side effects mentioned are also significantly reduced become.

The invention therefore relates to a process for the permanent deformation of keratin fibers, in which the fiber is treated with an aqueous preparation (A) of a keratin-reducing substance before and / or after mechanical deformation, rinsed out with water and / or an aqueous agent after an exposure time is then applied an aqueous preparation (B), then fixed after an exposure time with an aqueous preparation (C) of an oxidizing agent and optionally rinsed after an exposure time and optionally aftertreated, whereby preparation (B) at least one protein hydrolyzate and additionally one or more Contains amino acids.

Surprisingly, it was found that the application of a solution of protein hydrolyzate and additional amino acids after rinsing out the waving agent and before applying the fixation significantly improves the tensile / stretching property of the hair. The damage to the hair is reduced and the strength is increased.

The following terms are also used: "Corrugating agent" for the aqueous preparation (A) of the keratin-reducing

substance

"Care product" for the aqueous preparation (B) of protein hydrolyzate and additional amino acid

"Fixing agent" for the aqueous preparation (C) of the oxidizing agent.

These agents are used in the course of a process for the permanent shaping of keratin fibers and can contain all the constituents customary for these agents.

The method according to the invention for the permanent deformation of keratin fibers is preferably used for perming or straightening human hair. ι

The preparation (B) used according to the invention contains at least one protein hydrolyzate. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, the term protein hydrolyzates is understood to mean “polymers also built up from amino acids and amino acid derivatives. These include, for example, polyalanine, polyasparagine, polyserine, polyglycine, etc. Total hydrolysates of proteins are not to be understood by the term protein hydrolysates in the sense of the invention.

The protein hydrolyzates are preferably contained in the preparation (B) used according to the invention in amounts of 0.01 to 10% by weight. Amounts of 0.1 to 4% by weight are particularly preferred.

The protein hydrolyzates can be of vegetable, animal, marine or synthetic origin.

According to a particular embodiment, the preparation (B) used according to the invention contains vegetable and / or animal protein hydrolyzates Origin. One advantage of vegetable uride / or animal protein hydrolyzates is the particularly good biological compatibility of the products. i

Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example under the brands Dehylan ^® (Cognis), Promois ^® (Interorgana), Collapuron ^® (Cognis), Nutrilan ^® (Cognis), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda).

As protein hydrolysates of plant origin come e.g. B. Soybean, almond, pea, potato and wheat protein hydrolyzates into consideration. Such products are, for example, under the brand names Gluadin® ^® (Cognis), DiaMin® ^® (Diamalt) ^® (Inolex), Hydrosoy ^® (Croda), hydro Lupine ^® (Croda), hydro-Sesame ^® (Croda), hydro Tritium ^® (Croda) and Orotein ^® (Croda) available.

According to a particular embodiment, the care agent (B) contains keratin hydrolyzate. Keratin hydrolyzate has the particular advantage that it is well absorbed on the hair and thereby helps to protect the hair and improve the structure.

According to one embodiment, the molecular weight of the protein hydrolyzates that can be used is between 500 and 200,000 daltons. The molecular weight is preferably 1000 to 50,000 and very particularly preferably 1000 to 10,000 Daltons.

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon® ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^® (Croda). The amino acid additionally contained in the care product (B) used according to the invention can be used both as a free amino acid and as a salt, e.g. B. as hydrochloride or alkali or ammonium salt. The amino acid can be in both D and L form.

According to a particular embodiment, the content of additional amino acids in preparation (B) is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 4% by weight and in particular 1 to 2.5% by weight. %.

According to another embodiment of the process according to the invention, at least one of the amino acids additionally contained in preparation (B) is selected from histidine, arginine or lysine, in particular histidine. In addition to the carboxylic acid and amino functions on the α-C atom, these amino acids carry a further basic imidazolinium, guanidinium or ammonium group in the side chain.

According to a further preferred embodiment of the method according to the invention, the ratio of amino acid to protein hydrolyzate contained in preparation (B) in% by weight is 1: 0.01 to 1:10, with 1: 0.1 to 1: 3 being particularly preferred.

Treatment of the hair with the care agent (B) used according to the invention after rinsing out the wave agent (A) improves the tensile / stretching property of the treated hair. The hair structure of the cortex is less damaged compared to the values without care treatment or only with protein hydrolyzate.

The care agent (B) preferably has a pH between 3 and 9, and in particular from 4 to 7, e.g. 6.3, on.

The care product (B) used according to the invention can also be rinsed out of the hair after the exposure time before the fixative (C) is applied. i ^' ,

The direct application of fixative (C) after the contact time of the care product (B) is preferred. ^■

According to a further particular embodiment of the method according to the invention, preparation (B) is in the form of a concentrate or powder which is diluted with water or dissolved and / or suspended in water before use in order to obtain the ready-to-use preparation.

The preparations (A, B, C) used according to the invention can also be formulated as a cream, gel or liquid. Furthermore, it is possible to assemble the agent in the form of foam aerosols, which are mixed with a liquefied gas such. B. propane-butane mixtures, nitrogen, CO ₂ , air, NO2, dimethyl ether, chlorofluorocarbon blowing agents or mixtures thereof are filled in aerosol containers with a foam valve. The individual components of the method according to the invention are preferably used as a cream, gel or liquid.

All aqueous preparations of the process according to the invention can also be made from two different components, e.g. in the case of preparation (A) from a corrugated solution and a care component. Furthermore, the care product (B), the corrugation product (A) and / or the fixation (C) as such can already be in two or more phases.

Two-phase and multi-phase systems are systems in which there are at least two separate, continuous phases. For example, in such systems an aqueous phase and one or more e.g. two, non-miscible, non-aqueous phases are present separately from each other. Likewise possible are, for example, a water-in-oil emulsion and an aqueous phase present separately therefrom or a water-in-oil emulsion and a separate aqueous phase present.

The aqueous and the non-aqueous phases lie in the agents used in the process according to the invention, the waving agent (A), the Care product (B) and the fixation (C), in proportions (based on the weight) of 1: 200 to 1: 1, preferably from 1:40 to 1: 5 and particularly preferably from 1:20 to 1:10. In cases where there are several non-aqueous phases, this information refers to the total of the non-aqueous phases.

The wave agents (A) used according to the invention contain the mercaptans known as keratin-reducing substances.

According to a particular embodiment, the keratin-reducing substances are ^" selected ^" from ^_ thioglycolic acid, thiolactic acid, thio malic acid, mercaptoethanesulfonic acid and their salts and esters, cysteamine, cysteine, multicolored salts and salts of sulfurous acid and mixtures thereof. The alkali metal or ammonium salts of thioglycolic acid, thio malic acid and / or thiolactic acid are particularly suitable.

The keratin-reducing substances are preferably used in the waving agents (A) in concentrations of 0.3 to 2.0 mol / kg at a pH of 5 to 12, in particular from 7 to -9.5. Mixtures of salts of thioglycolic acid and salts of thiolactic acid can be preferred. To adjust this pH

The waving agents (A) usually contain alkalizing agents such as ammonia, alkali and ammonium carbonates and hydrogen carbonates or organic amines such as monoethanolamine.

The exposure time of the waving agents (A) to the hair is generally 5 to 40 minutes, the thickness of the hair to be treated, the condition of the hair, the desired degree of deformation, the size of the mechanical deformation aid used (hair roller) and the type of keratin reducing agent being further influencing factors are.

Heterocyclic compounds such as, for example, derivatives of imidazole, pyrrolidine, piperidine, dioxolane, dioxane, morpholine and piperazine can be used as further care substances in the aqueous wave agent (A). Also suitable derivatives of these compounds such as, for example, the C ₄ alkyl derivatives, C 1 hydroxyalkyl derivatives and C 1 -C ₄ aminoalkyl derivatives. Preferred substituents which can be positioned both on carbon atoms and on nitrogen atoms of the heterocyclic ring systems are methyl, ethyl, β-hydroxyethyl and β-aminoethyl groups. These derivatives preferably contain one or two of these substituents.

Derivatives of heterocyclic compounds preferred according to the invention are, for example, 1-methylimidazole, 2-methylimidazole, 4 (5) -methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-isopropylimidazole, N-methylpyrrolidone, 1-methylpiperidine, 4-methylpiperidine, 2- Ethyl piperidine, 4-methylmorpholine, 4- (2-hydroxyethyl) morpholine, 1-ethylpiperazine, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine. Imidazole derivatives which are further preferred according to the invention are biotin, hydantoin and benzimidazole. Among these heterocyclic care substances, the mono- and dialkylimidazoles, biotin and hydantoin are particularly preferred.

In addition, it can prove to be advantageous if penetration aids and / or swelling agents are contained in the wave means (A). These include, for example, urea and urea derivatives, guanidine and its derivatives, water glass, imidazole and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, hydrogen carbonates, diols and triols, and in particular 1,2- Diols and 1, 3-diols as described for example below under the term polyols. The penetration aids and swelling agents are contained in the preparations used according to the invention in amounts of 0.1 to 20% by weight. Amounts of 0.1 to 10% by weight are preferred.

Furthermore, the corrugating agents used according to the invention can contain corrugation-strengthening components, in particular urea, imidazole and the above-mentioned diols. Reference is expressly made to the publications DE-OS 44 36 065 and EP-B1-363 057. The waving power Compounds can be contained in the waving agents used according to the invention in amounts of 0.5 to 5% by weight, in particular 1 to 4% by weight.

The active substances described below can be used particularly advantageously within the scope of the invention as further constituents of both the corrugating agent (A) and the care agent (B) and / or the fixation (C).

The active substances are polyols, in particular glycerol and partial glycerol ether, 2-ethyl-1,3-hexanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, pentanediols, for example 1,2 -Pentanediol, hexanediols, for example 1, 2-hexanediol or 1, 6-hexanediol, dodecanediol, in particular 1,2-dodecanediol, neopentyl glycol and ethylene glycol are suitable. In particular, 2-ethyl-1,3-hexanediol, 1,2-propanediol, 1,3-propanediol and 1,3-butanediol have proven to be particularly suitable.

These polyols are preferably contained in the waving agents used according to the invention in amounts of 1 to 10, in particular 2 to 10,% by weight.

Also suitable are alcohols, in particular in multiphase systems, which are not more than 10% by weight soluble in water at 20 ° C., based on the mass of water.

Fatty substances such as fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components can be used as further care substances.

Linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms in amounts of 0.1 to 15% by weight, based on the total agent, can be used as fatty acids. Saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ to C ₃₀ - 'carbon atoms in amounts of 0.1 to 30 wt .-%, based on the entire preparation.

Natural and synthetic cosmetic oil bodies which can be used according to the invention are in particular:

- vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, wheat germ oil and the liquid components of coconut oil and triglyceride oils (for example the liquid components of beef tallow or synthetic triglyceride oils). ^■

liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, Qi-n nonyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether and n-decyl-n-undecyl ether as well as di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-rentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products 1, 3-di- (2-ethyl-hexyl) -cyclbhexan (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred.

The amount of natural and synthetic cosmetic oil bodies used in the agents used according to the invention is usually 0.1 to 30% by weight, based on the total agent, preferably 0.1 to 20% by weight, and in particular 0.1 to 15% by weight .-%.

The total amount of oil and fat components in the agents used according to the invention is usually 0.1 to 75% by weight, based on the total agent. Amounts of 0.1 to 35% by weight are preferred.

Furthermore, it has been shown that polymers are advantageously used in the process according to the invention. In a preferred embodiment, polymers are therefore added to the agents used according to the invention, both cationic, anionic, amphoteric and nonionic polymers having proven to be effective. Cationic polymers are understood to mean polymers which have a group in the main and / or side chain and which have a cationic group as a function of or independently of the pH of the agent. Polymers in which the quaternary ammonium group is bonded via a C1-4 hydrocarbon group to a polymer main chain composed of acrylic acid, methacrylic acid or their derivatives have proven to be particularly suitable.

Homopolymers of the general formula (I),

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ⁴ are selected independently of one another from Ci ^ alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically compatible organic or inorganic anion (for example halide ions, sulfate ions, phosphate ions, methosulfate ions as well as organic ions such as lactate, citrate, tartrate and acetate ions, and copolymers consisting essentially of those in formula (I ) Monomer units and nonionic monomer units listed are particularly preferred cationic polymers, preferred in the context of these polymers are those for which at least one of the following conditions applies: R ¹ stands for a methyl group, R ² , R ³ and R ⁴ stand for methyl groups; has the value 2. Preferred anions are halide ions, in particular chloride.

A particularly suitable homopolymer is that which may also be crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallylpolyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, Arabitol, mannitol, sorbitol, sucrose or glucose. Methylene bisacrylahiide is a preferred cross-linking agent.

I

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight.

Copolymers with monomer units of the formula (I) preferably contain, as nonionic monomer units, acrylamide, methacrylamide, C ₄ alkyl acrylate and C ₄ alkyl methacrylate. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer, in particular in a weight ratio of about 20:80.

Other preferred cationic polymers are, for example

- Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives,

cationic alkyl polyglycosides (according to DE-PS 44 13 686), cationized honey and cationic guar derivatives,

- polysiloxanes with quaternary groups, which are particularly preferred conditioning agents, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamo- dimethicone), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified Silicon, which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, quaternium -80)

polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, for example Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer), - Copolymers of vinyl pyrrolidone, in particular with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, with

1

Diethyl sulfate quaternized vinyl pyrrolidone-dimethylaminoethyl methacrylate copolymers,

Vinylpyrrolidone-vinylimidazolium methochloride copolymers,

- quaternized polyvinyl alcohol,

- as well as those under the names Polyquatemium 2, Polyquaternium 17,

Polyquaternium 18, Polyquaternium 24 and Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain,

- Chitosan and its derivatives.

The preferred anionic polymers predominantly contain carboxylate and / or sulfonate groups. Examples of corresponding anionic monomers are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropane sulfonic acid, which can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-rήethylpropansulfonsäure and acrylic acid (for example, as Rheotik ^® 11-80 commercially available).,.

It may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone, vinyl ether and vinyl ester.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. These copolymers can also be crosslinked, the crosslinking agents used preferably being polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene bisacrylamide. Also preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene can be preferred crosslinking agents (available under the Carbopol ^® brand, for example).

Ampho-polymers are also suitable as conditioning agents. Under the generic term amphoteric polymers are amphoteric polymers, i. H. Polymers which contain both free amino groups and free -COOH or SOaH groups in the molecule and are capable of forming internal salts are zwitterionic

Polymers which contain quaternary ammonium groups and -COO "- or -SO ₃ " - groups in the molecule and those polymers which contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of ethyl methacrylate tert-butylamino, N- (1, 1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters.

Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers, as for example in German Laid-open specification 39 29 973 and the state of the art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N and the commercial product Merquat ^® 280, are particularly preferred amphopolymers according to the invention.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also very suitable polymers (for example Stabileze ^® QM crosslinked with 1, 9-decadienes). Furthermore, nonionic polymers can be contained in all aqueous preparations of the process according to the invention. It may be preferred to use this in the fixation (C). .

Suitable nonionic polymers are, for example:

Vinylpyrrolidone / Vinylester copolymers, for example, Luviskol ^® (BASF), cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropylcellulose,

- Shellac

- polyvinylpyrrolidones,

- Water-soluble as well as water-insoluble siloxanes. Both volatile and non-volatile siloxanes are suitable, non-volatile siloxanes being understood to mean those compounds whose boiling point at normal pressure is above 200 ° C. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups.

- Glycosidically substituted silicones according to EP 0612759 B1.

It is also possible according to the invention that the preparations used contain several, in particular two different polymers of the same charge and / or each contain an ionic and an amphoteric and / or nonionic polymer.

The polymers are preferably present in the agents used according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts from 0.1 to 5, in particular from 0.1 to 3% by weight are particularly preferred.

Furthermore, 2-pyrrolidinone-5-carboxylic acid and / or its derivatives can be used in the preparations of the process according to the invention. Preferred are the sodium, potassium, calcium, magnesium or ammonium salts, in which the ammonium ion, in addition to hydrogen, has one to three C 1 -C ₄ -alkyl groups wearing. The sodium salt is very particularly preferred. The amounts used in the agents used according to the invention are 0.05 to 10% by weight, based on the total agent, particularly preferably 0.1 to 5 and in particular 0.1 to 3% by weight.

The use of vitamins, provitamins and vitamin precursors and their derivatives has also proven to be advantageous.

Vitamins, pro-vitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred.

The group of substances called vitamin A includes retinol (vitamin Ai) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. Possible vitamin A components are, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A _τ alcohol and its esters such as palmitate and acetate. The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05 to 1% by weight, based on the overall preparation.

The vitamin B group or the vitamin B complex include u. a.

- Vitamin Bi (thiamine)

- Vitamin B ₂ (riboflavin)

- Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. According to the invention, preference is given to nicotinic acid amide, which is preferably present in the agents used according to the invention in amounts of 0.05 to 1% by weight, based on the total agent.

- Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, the panthe- nolmonoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin Bs type mentioned are preferably present in the agents used according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

- Vitamin Bβ (pyridoxine and pyridoxamine and pyridoxal),

- Vitamin C (ascorbic acid). Vitarnin C is preferably used in the agents used according to the invention in amounts of 0.1 to 3% by weight, based on the total agent. Use in the form of the palmitic acid ester, the glucosides or phosphates can be preferred. Use in combination with tocopherols may also be preferred.

- Vitamin E (tocopherols, especially tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the agents used according to the invention in amounts of 0.05 to 1% by weight, based on the agent as a whole ,

- Vitamin F. The term “vitamin F” usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

- Vitamin H. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexa- hydrothienol [3,4-d] imidazole-4-valeric acid, for which the trivial name biotin has now become established. Biotin is contained in the agents used according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

The preparations used according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, E and H.

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.

In addition, plant extracts and mixtures thereof can be used in the preparations of the method according to the invention. Especially for them The extracts from chamomile, witch hazel, green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, linden flowers and melon are suitable for use in accordance with the invention.

The extracts are generally produced. by extracting individual parts of plants or the entire plant. Water, alcohols and mixtures thereof can be used as extractants. Among the alcohols, ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used both in pure and in diluted form.

Further constituents of all aqueous preparations can be surface-active compounds, in particular those from the group of anionic, amphoteric, zwitterionic and / or nonionic surfactants.

The term surfactants is understood to mean surface-active substances which form adsorption layers on surfaces and interfaces or which can aggregate in volume phases to form micelle colloids or lyotropic mesophases.

Suitable anionic surfactants in preparations used according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by an anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, - linear and branched fatty acids with 8 to 30 carbon atoms. Atoms (soaps), Ether carboxylic acids of the formula R-0- (CH ₂ -CH ₂ 0) _x -CH ₂ -COOH, in which R is a linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16, acyl sarcosides, acyl taurides or acyl isethionates with 8 to 24 carbon atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters with 8 to 24 carbon atoms in the alkyl group and the corresponding sulfosuccinic acid mono-alkylpolyoxyr ethyl esters with 1 to 6 oxyethyl groups, linear alkane sulfonates and linear alpha-olefin sulfonates with 8 to 24 carbon atoms,

Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH ₂ -CH ₂ 0) _x - OS0 ₃ H, in which R is a preferably linear alkyl group with 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 hydroxyalkyl and / or hydroxyalkylene propylene glycol ethers

DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 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 which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols with 8 to 22 carbon atoms, alkyl and / or alkenyl ether phosphates of the formula, monoglyceride sulfates and monoglyceride ether sulfates of the formula (III)

(III)

in which R ⁸ CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 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 as well as their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates of the formula (III) are preferably used, in which R ⁸ CO stands for a linear acyl radical having 8 to 18 carbon atoms.

Amidether carboxylic acids as described in EP 0 690 044,

- Sulphated fatty acid alkylene glycol esters of the formula (II) R ⁷ CO (AlkO) _n Sθ ₃ M, in which R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n is a number from 0.5 to 5 and M is a cation, as described in DE-OS 197 36 906.5,

- condensation products of C ₈ - C ₃₀ - fatty alcohols with protein hydrolysates and / or amino acids and their derivatives, which are known to the expert as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - Types ,

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, monoglycer disulfates, alkyl and alkenyl ether phosphates and

Protein fatty acid condensates.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SOs ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl- 3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkynaminopropionic acids and alkylamino acetic acids 8 with f ^~ up to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C ₁₂ -C ₈ -acyl sarcosine.

Nonionic surfactants contain e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such connections are, for example

Adducts of 2 to 50 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear and branched fatty alcohols or fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,

- With a methyl or C2-C ₆ alkyl group end-capped adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,

Ci ₂ -C ₃ o fatty acid monoesters and diesters of adducts of 1 to 30 mol of ethylene oxide with glycerol, adducts of 5 to 60 mol of ethylene oxide with castor oil and hardened castor oil (can also be used as an emulsifier) and alkoxylated triglycerides,

Polyol fatty acid esters, alkoxylated fatty acid alkyl esters of the formula (IV)

R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (IV) in which 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 a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands,

Amine oxides,

Hydroxy mixed ethers, as described, for example, in DE-OS 19738866,

- sorbitan and sugar fatty acid esters,

- Addition products. from ethylene oxide to sugar fatty acid esters, sorbitan fatty acid esters such as polysorbates, fatty acid alkanolamides

^" and fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type according to the formula (V) R ⁴ 0- [G] _p ,

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 which can be obtained by the process known in the literature.

The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VI) 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 an integer and here can assume all the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can differ from primary alcohols with 4 to 11, preferably 8 to Derive 10 carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, from hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -Cιo (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the distillative separation of technical C ₈ -C ₈ coconut oil and with a proportion of less than 6

% By weight of Ci ₂ 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 their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened Ci ₂ / i ₄ coco alcohol with a DP of 1 to 3 are preferred.

- Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamide type, a nonionic surfactant of the formula (VI), R ⁶

₅ IR ⁵ CO-N- [Z] (VI) in which R ⁵ CO is 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 one or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. 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 production, reference is made, for example, to international patent application WO 92/06984. Lead preferably the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars with 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 (VII):

R ⁸ OH OH OH

I I I I

R ⁷ CO-N-CH ₂ -CH-CH-CH-CH-CH ₂ OH (VII)

I OH

The preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (VII) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or, erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (VII) 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 are particularly preferred. The polyhydroxyalkylamides can also be derived from maltose and palatinose.

The alkylene oxide adducts with saturated linear fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, have proven to be preferred nonionic surfactants. Fatty acid esters of ethoxylated glycerol are also preferred. The branched alkyl radical R preferably contains 6 to 22 carbon atoms. Primary linear and methyl-branched aliphatic radicals in the 2-position are particularly preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These can be in the agents used according to the invention preferably in amounts of 0.1 to 20% by weight. Amounts from 0.5 'to 15% by weight are preferred, and particularly preferably from 0.5 to 7.5% by weight. i

The surfactants are used in amounts of 0.1 to 45% by weight, preferably 0.5 to 30% by weight and very particularly preferably 0.5 to 25% by weight.

Emulsifiers are preferably used in the preparations of the method according to the invention. Emulsifiers cause water or oil-stable adsorption layers to form at the phase interface, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. An emulsion is to be understood as a droplet-like distribution (dispersion) of a liquid in another liquid with the expenditure of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers is based on the substances to be dispersed and the particular external phase as well as the fine particle size of the emulsion. Emulsifiers which can be used according to the invention are, for example

- Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with inert fatty alcohols. With-8. up to 22 C atoms, -on fatty acids with 12 to 22 C atoms and on alkylphenols with 8 to 15 C atoms in the alkyl group,

- C ₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with polyols having 3 to 6 carbon atoms, in particular with glycerol,

- Ethylene oxide and polyglycerol adducts with methylglucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, degrees of oligomerization of 1.1 to 5, in particular 1.2 to 2.0, and glucose as the sugar component being preferred,

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

Partial esters of polyols with 3 to 6 carbon atoms with saturated fatty acids with 8 to 22 C atoms, - sterols. Sterols are understood to be a group of steroids which carry a hydroxyl group on the C atom 3 of the steroid structure and both from animal tissue (zoosterols such as lanosterol and cholesterol) and from vegetable fats (phytosterols, for example ergosterol, stigmasterol and sitosterol) be isolated. Sterols, the so-called mycosterols, are also isolated from fungi and yeasts.

- phospholipids. These include primarily the glucose phospholipids, e.g. as lecithins or phosphatidylcholines from e.g. Egg yolks 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, for example, polyglycerol poly-12-hydroxystearate,

- Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents used according to the invention preferably contain the emulsifiers in amounts of 0.1 to 25% by weight, in particular 0.1 to 3% by weight, based on the total agent.

The compositions used according to the invention can preferably contain at least one nonionic emulsifier with an HLB value of 8 to 18, according to the 10th edition, Georg Thieme Verlag Stuttgart, New York, in Römpp Lexikon Chemie (Ed. J. Falbe, M. Regitz) , (1997), page 1764. Nonionic emulsifiers with an HLB value of 10 to 15 can be particularly preferred according to the invention.

The fixing agents (C) used according to the invention contain oxidizing agents, for example sodium bromate, potassium bromate, hydrogen peroxide and the stabilizers customary for stabilizing aqueous hydrogen peroxide preparations. The pH of such aqueous H 0 ₂ preparations, which usually contain about 0.5 to 15% by weight, usually about 0.5 to 3% by weight, H ₂ O ₂ ready for use, is preferably 2 to 6, in particular 2 to 4; it is adjusted by acids, preferably phosphoric acid, phosphonic acids and / or dipicolinic acid. As part of the The method according to the invention is possible and it may be preferred to use a larger volume of the preparation (C) with comparatively lower H ₂ 0 ₂ concentrations, in particular in the range from 0.5 to 1.5% by weight, of the required amount of H ₂ 0 ₂ .-% to use. Bromate-based fixatives usually contain the bromates in concentrations of 1 to 10% by weight and the pH of the solutions is adjusted to 4 to 7. According to the invention, the use of fixative concentrates which are diluted with water before use can be particularly preferred.

Furthermore, it is possible to carry out the oxidation with the aid of enzymes, where ^"the enzymes both to produce oxidizing per compounds are used as well as to enhance the effect of a small amount of oxidizing agents, or enzymes are used, the electrons from suitable developer Components (reducing agents) to atmospheric oxygen, preferably oxidases such as tyrosinase, ascorbate oxidase and laccase, but also glucose oxidase, uricase or pyruvate oxidase, and the procedure, the effect of small amounts (eg 1% and less) of hydrogen peroxide amplified by peroxidases.

The fixatives can of course also be formulated as solids. They then contain the oxidizing agent in the form of a solid, e.g. Potassium or sodium bromate and water and / or nourishing ingredients are added shortly before use. It is also possible and preferred to formulate the oxidizing agent as a two-component system. The two components, one of which is preferably a hydrogen peroxide solution or an aqueous solution of another oxidizing agent and the other of which contains the other constituents, in particular caring substances and / or reducing agents, are then mixed only shortly before use.

Furthermore, it is preferred to use hydroxycarboxylic acids and in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids and also the dihydroxy, trihydroxy and polyhydroxydi, tri and polycarboxylic acids in the fixation (C). It has been shown that in addition to the Hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Other basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols with 8-22 C atoms, for example fatty alcohols or synthetic fatty alcohols. The esters of Ci ₂ -C ₅ fatty alcohols are particularly preferred. Esters of this type are commercially available, for example under the brand Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxy polycarboxylic acids are polylactic acid and poly-tartaric acid and their esters. ι

In addition to the components already mentioned, the fixing agents can contain, as surface-active compounds, cationic surfactants of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with Diethanolalkylamines and quaternized 'ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines.

I

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. The stearamidopropyldimethylamine available as Tegoamid ^® S 18 is particularly suitable.

The agents used according to the invention preferably contain the cationic surfactants in amounts of 0.05 to 10% by weight. Amounts of 0.1 to 5% by weight are particularly preferred.

Suitable conditioning agents in all agents used according to the invention are: silicone oils and silicone gums, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200 and DC 1401 products sold and the commercial product Fancorsil ^® LIM first A suitable anionic silicone oil is the product Dow Corning ^® 1784.

Other active ingredients, auxiliaries and additives are, for example

Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

- perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides, such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate,

- defoamers like silicones,

Dyes for coloring the agent, pigments,

- anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,

- Active ingredients such as allantoin and bisabolol as well as antioxidants

- cholesterol,

- consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

- fats and waxes such as walrus, beeswax, montan wax and paraffins,

- fatty acid alkanolamides,

^~ - complexing agents such as EDTA, NTATß-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as primary, secondary and tertiary phosphates,

- opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescent agents such as ethylene glycol mono- and distearate and PE, G-3 distearate,

- Substances to adjust and keep the pH constant

A second object of the invention is the use of at least one protein hydrolyzate and additionally one or more amino acids in a ^"preparation (B) in the inventive process for the permanent deformation of keratinous fibers.

The invention further relates to a kit for use in a method according to the invention, which comprises at least one keratin-reducing preparation (A), one fixing preparation (C) and one preparation (B) which contains at least one protein hydrolyzate and additionally one or more amino acids, exists, the preparations being packed separately.

The following examples are intended to explain the invention in more detail without restricting it thereto. Examples

Application:

The hair cross sections for 40 moistened individual hairs (type: Natural dark brown; code # 6634, Alkinco) were determined. The gradient was then measured in the Hook range up to 1% elongation of the untreated hair. The tensile strain measurements were carried out with a fully automatic MTT 670 from Dia Stron.

The waving agent A was then applied to the hair. After a contact time of 20 minutes, the hair was rinsed thoroughly with tap water for 5 minutes. The care product (B) was applied to damp hair and after a contact time of 10 minutes, fixative C was applied to the hair. The hair was fixed for 10 minutes and then the hair was rinsed with water for 5 minutes. The same measurements were then carried out on the treated hair as before on the untreated hair.

Due to the non-destructive measurement method, a difference measurement could be carried out on a single hair between the untreated and treated condition. The evaluation was carried out by means of covariance analysis.

Reducing preparation (A)

7% thioglycolic acid

3.5% ammonium carbonate

0.3% hydroxethane-1,1-diphosphonic acid pH 8.4 Care products (B)

Bi test: 2 wt .-% Nutrilan Keratin W ^® (Cognis), 1 wt .-% histidine,

Balance water, pH 6.3

B? Reference: 2 wt .-% Nutrilan Keratin W ^® (Cognis), residual water, pH 6.3

Fixation (C)

2% hydrogen peroxide

1% hydroxethane-1, 1-diphosphonic acid pH, O ^{■ •} - -

The percentage given above indicates the percentage probability with which the series of measurements are distinguished. If the value is> 95%, the series of measurements can be regarded as significantly different.

Claims

claims:

1. A process for the permanent deformation of keratin fibers, in which the fiber is treated with an aqueous preparation (A) of a keratin-reducing substance before and / or after mechanical deformation, is rinsed out with water and / or an aqueous agent after an exposure time, then one aqueous preparation (B) is applied, then fixed after an exposure time with an aqueous preparation (C) of an oxidizing agent and optionally rinsed after an exposure time and optionally aftertreated, where preparation (B) contains at least one protein hydrolyzate and additionally one or more amino acids ,

2. The method according to claim 1, characterized in that the preparation (B) contains between 0.01 and 10 wt .-%, in particular between 0.1 and 4 wt .-% protein hydrolyzate.

3. The method according to claim 1 or 2, characterized in that the protein hydrolyzates contained in the preparation (B) are of vegetable and / or animal origin.

4. The method according to claim 3, characterized in that the preparation (B) contains keratin hydrolyzate.

5. The method according to any one of claims 1 to 4, characterized in that the average molecular weight is between 500 and 200,000 daltons and in particular between 1000 and 10,000 daltons.

6. The method according to any one of claims 1 to 5, characterized in that at least one of the amino acids additionally contained in the preparation (B) is selected from histidine, arginine and / or lysine, in particular histidine.

7. The method according to any one of claims 1 to 6, characterized in that the content of additional amino acids in the preparation (B) is 0.1 to 10 wt .-%, in particular 0.5 to 4 wt .-%.

8. The method according to any one of claims 1 to 7, characterized in that the ratio of amino acid to protein hydrolyzate in preparation (B) in wt .-% 1: 0.01 to 1:10, in particular 1: 0.1 to 1: 3 is.

9. The method according to any one of claims 1 to 8, characterized in that the preparation (B) is in the form of a concentrate or powder which is diluted with water or dissolved therein before use.

10. The method according to any one of claims 1 to 9, characterized in that the keratin-reducing substance is selected from thioglycolic acid, thiolactic acid, thio malic acid, mercaptoethanesulfonic acid and their salts and esters, cysteamine, cysteine, multicolored salts and salts of sulfurous acid and mixtures thereof.

11.Use of at least one protein hydrolyzate and one or more additional amino acids in a preparation (B) in a process for the permanent deformation of keratin fibers according to one of claims 1 to 10.

12. Kit for use in a method according to any one of claims 1 to 10, characterized in that it consists of at least one keratin-reducing preparation (A), a fixing preparation (C) and a preparation (B), the at least one protein hydrolyzate and additionally one contains or contains several amino acids.