DE19855606A1 - Means for permanent deformation of keratin fibers - Google Patents

Abstract

The invention relates to agents for permanently shaping keratin fibers. Said agents contain, in an aqueous preparation with a pH of 6 to 9.5, at least one water-soluble sulfite, bisulfite or hydrogen sulfite in the form of their alkali, alkaline earth or ammonium salts in an amount of 2-15 wt.-%, based on the entire agent, at least one thio compound in an amount of 0.01-5 wt.-%, based on the entire agent, and at least one protein derivative. The inventive agents are characterized by an improved care effect while having a good waving effect.

Description

This invention relates in particular to agents for permanent deformation of keratin fibers of human hair and their use.

The permanent deformation of keratin fibers is usually carried out in such a way that the fiber is mechanically deformed and the deformation is fixed using suitable aids sets. Before and / or after this deformation, the fiber is treated with the aqueous additive preparation of a keratin-reducing substance (waving agent) and rinses after soaking time with water or an aqueous solution. In a second step you deal with then the fiber with the aqueous preparation of an oxidizing agent (fixing agent). To After an exposure time, this is also rinsed out and the fibers are removed from the mechanical Deformation aids (curlers, papillots) are exempt. Alternatively, the fiber already released from the mechanical deformation aids after half the exposure time become. After the post-fixation, the oxidizing agent becomes thorough rinsed out.

The wave agent is usually alkaline, so that the fiber swells and on this Way allows a deep penetration of the keratin-reducing substance into the fiber becomes. The keratin-reducing substance cleaves part of the disulfide bonds of the Keratins to -SH groups so that there is a loosening of peptide crosslinking and as a result the tension of the fiber due to the mechanical deformation to a new orientation of the Keratin texture comes. Under the influence of the oxidizing agent, disulfide  Bonds are made, and in this way the keratin structure is given in the predetermined Deformation fixed.

A known method of this type is permanent wave treatment of human hair This can be used to create curls and waves in straight hair as well can be used to straighten curly hair.

Although this procedure, which is referred to as perm, is used on a large scale today is applied, it cannot yet be optimal in terms of several parameters be considered.

The so-called "strength" is decisive for achieving the desired forming of the waving agent, by the amount and type of reducing agent as well as the alkalinity of the wave agent can be influenced. Corrugating agent that is a satisfactory Guarantee forming performance, but can be used in stressed, especially oxidative pretreated, hair damage to breakage. Also can in Problems in the scalp area occur in individual cases.

Mercaptans are usually used as keratin-reducing substances. This are characterized by a good corrugation effect. Nevertheless, the reducing agents have the Disadvantage that they attack the hair relatively strongly and also a bad smell exhibit. To solve this problem has therefore been tried for a long time, the Mercaptans by other reducing agents, e.g. B. to replace by sulfites. Corrugating agents, the contain as the only reducing agent sulfites, have a significantly lower Odor and less hair damage, but often leave in terms of your wave power still needs.

In EP-B1-257 256 it was therefore proposed to combine one water-soluble mercaptans with a water-soluble sulfite, bisulfite or hydrogen sulfite under certain conditions to obtain a corrugated solution that has good corrugation at the same time causes less damage to the fibers.  

Nevertheless, even this procedure can not yet with regard to the care effect for the Fibers convince.

The present invention was therefore based on the object of low odor To provide corrugating agents that have good corrugating power as well as low Damage to the fibers guaranteed.

It has now been found that with the aid of a novel combination of active ingredients permanent deformation of keratinic fibers are available, which are characterized by improved usage properties and a significantly increased tolerance distinguish constant wave effectiveness. With the help of the agents according to the invention there is significantly less damage to human hair with almost the same Well stability.

A first object of the invention are therefore agents for permanent deformation of keratinic fibers, which are in aqueous preparation at a pH of 6 to 9.5

• A) at least one water-soluble sulfite, bisulfite or hydrogen sulfite in the form of Alkali, alkaline earth or ammonium salt in an amount of 2-15% by weight, based on the whole average,
• B) at least one thio compound in an amount of 0.01-5 wt .-%, based on the whole mean
• C) at least one protein derivative

included, with the proviso that the amount of component (A) is greater than on average the amount of component (B).

According to the invention, keratin fibers include furs, wool, feathers and in particular understand human hair. The details of the teaching of the invention will be described below using permanent wave agents. However, the teaching is suitable in to the same extent and with the same advantages for smoothing naturally curled or chemically wavy hair.

The first component (A) of the reducing agent combination according to the invention are water soluble sulfites. These are essentially the alkali, alkaline earth and / or  Ammonium salts of sulfites, bisulfites, and / or hydrogen sulfites, e.g. B. the sodium or Potassium bisulfite. The have been particularly effective in the sense of the invention Ammonium salts of bisulfites and / or hydrogen sulfites have been proven.

A thio component is used as component (B). Under a thio component a compound is understood according to the invention which has at least one free thiol group having.

Glutathione, dithiothreitol, cysteamine and cysteine and their are particularly effective physiologically acceptable salts. As cysteine salts of a physiologically acceptable acid are understood their products of addition to cysteine. As physiologically acceptable Acids are, for example, acetic acid, lactic acid, citric acid and oxalic acid, but also inorganic acids, such as sulfuric acid or hydrochloric acid.

Particularly preferred components (B) are the cysteine and the cysteine salts physiologically acceptable acid, especially the cysteine hydrochloride.

In a preferred embodiment, the wave agents according to the invention contain as Component (A) ammonium bisulfite and as component (B) cysteine hydrochloride, for example in the form of the monohydrate.

The agents according to the invention contain a third mandatory component (C) Protein derivative. The protein derivatives can be based on animal or vegetable proteins based. Suitable starting materials are, for example, keratin, collagen, elastin, Wheat proteins, milk proteins, protein proteins, silk proteins, almond proteins, Soy proteins and proteins from animal skins.

The corresponding protein hydrolyzates are then each made as a product mixture from the acidic, basic and / or enzymatically catalyzed degradation of these proteins.

Cationic derivatives are obtained by subsequent reaction with compounds which usually carry quaternary ammonium groups or by reaction with corresponding amines and subsequent quaternization. A number of such quaternary Protein hydrolyzates are available as commercial products, for example under the  Trade names Lamequat® L (cationic collagen hydrolyzate; INCI name: Lauryldimonium hydroxypropylamino hydrolyzed animal protein; Henkel), Croquat® WKP (animal keratin hydrolyzate; INCI name: Aqua, Cocodimonium hydroxypropyl hydrolyzed keratin; Croda GmbH), Hydrotriticum® QL (cationic Wheat protein hydrolyzate; INCI name: Lauryldimonium hydroxypropyl hydrolyzed wheat protein; Croda) and Crotein® Q (cationic collagen hydrolyzate; INCI- Name: Hydroxypropyltrimonium hydrolyzed collagen; Croda). For improvement Quaternized protein hydrolyzates are special for the nourishing effect of the waving agent prefers.

In a first preferred embodiment, protein derivatives are of animal origin prefers. The protein hydrolysates of animal keratin are particularly preferred. Since the Composition regarding the amino acid sequences involved that of human hair is very similar, there is a high affinity of such products for human hair.

However, it can also be according to a further embodiment of the present invention be preferred to use protein derivatives of vegetable origin.

Protein derivatives are usually in amounts of 0.2 to 5 wt .-% in the agents according to the invention used.

In a preferred embodiment of the invention, the means for permanent contain Deformation of keratin fibers to reinforce the wave effect continues to be a network and / or a penetrant. It can be particularly preferred to use both a wetting agent and also to use a penetrant in the agents according to the invention.

Suitable penetrants according to the invention are urea, imidazole, 1,3-butanediol, ethoxydiglycol and C ₂ - to C ₆ -polyols, such as propylene glycol or butylene glycol. Urea and imidazole are particularly preferred penetrants.

According to the invention, penetrants are used in amounts of 0.5 to 5% by weight, particularly preferably used in amounts of 1 to 3% by weight. Only urea is used in quantities from 5-30 wt .-%, in particular from 10 to 15 wt .-% used.

In principle, wetting agents according to the invention are all nonionic, anionic and cationic surfactants.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a poly lyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• - Adducts of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 to 22 carbon atoms Atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• C _12-22 fatty acid monoesters and diesters of adducts of 1 to 30 mol of ethylene oxide with glycerol,
• C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened rizi nut oil,
• Addition products of ethylene oxide onto sorbitan fatty acid esters,
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Alkyl polyglycosides according to formula (I)

R ¹ -O- (Z) _x (I)

in which R ¹ represents an alkyl radical having 8 to 22 carbon atoms, Z a mono- or oligosaccharide and x a number from 1.1 to 5, are nonionic surfactants which are particularly preferred according to the invention. These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 8 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R ^{1 are} mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Alkylpolyglycosides in which R ¹

• essentially from C ₈ and C ₁₀ alkyl groups,
• essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C ₁₆ alkyl groups or
• - consists essentially of C ₁₂ - to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Usually sugar with 5 or 6 carbon atoms and the corresponding Oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, Talose and sucrose. Preferred sugar components are glucose, fructose, galactose, Arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 Sugar units. Alkyl glycosides with x values from 1.3 to 2 are preferred. Be completely alkyl glycosides in which x is 1.4 to 1.6 are particularly preferred.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 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 as well as the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear fatty acids with 10 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 carbon atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bin solutions according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 Represent carbon atoms.

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, and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Examples of the cationic surfactants which can be used in the agents according to the invention are especially quaternary ammonium compounds. Am are preferred monium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chloride and trialkylmethyl ammonium chloride, e.g. B. cetyltrimethylammonium chloride, Stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammoni umchloride.

Alkylamidoamines, especially fatty acid amidoamines like the one under the name Tego Amid®S18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as those sold under the trademark Stepantex® Methyl-hydroxyalkyldialkoyloxyalkyl-ammonium methosulfate and those under the Trademark Dehyquart® products such as Dehyquart AU-46 or Dehyquart L80.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided is the commercial product Glucquat®100, according to INCI nomenclature a "Lauryl Methyl Glu ceth-10 hydroxypropyl dimonium chloride ".

The compounds with alkyl groups used as surfactants can in each case be act uniform substances. However, it is usually preferred in the manufacture these substances from natural vegetable or animal raw materials, so that one Mixtures of substances with different ones depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the adducts of ethylene and / or propylene oxide with fatty alcohol represent alcohols or derivatives of these addition products, both products with a "normal" homolog distribution as well as those with a narrowed homolog distribution can be used. Under "normal" homolog distribution, Mi understandings of homologues used in the implementation of fatty alcohol and  Alkylene oxide using alkali metals, alkali metal hydroxides or alkali receives metal alcoholates as catalysts. Narrowing homolog distributions will be on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution can be preferred.

The wetting agents in the agents according to the invention are preferably in amounts of 0.2 to 10% by weight, in particular about 0.5 to 5% by weight, in each case based on the total composition, in front.

In a further preferred embodiment, the means for permanent Deformation of keratin fibers also contain another conditioning agent. This leads to a significantly improved condition of the hair after application of the inventive wave agents compared to conventional agents.

Conditioning agents according to the invention are amino acids and cationic polymers. In principle, however, the quaternaries listed as cationic surfactants are also Ammonium compounds have a hair conditioning effect.

The basic and neutral ones are particularly effective as conditioning agents Amino acids. Preferred amino acids according to the invention are arginine, lysine, glycine, Serine, tryptophan and alanine.

Suitable conditioning agents contain cationic polymers within the Polymeric backbone cationic groups. These groups can be part of the polymer chain, but they can also be located in side chains, which are connected by intermediate links with a Main chain are connected. Common cationic groups contain quaternary nitrogen or phosphorus atoms. Groups with quaternary nitrogen atoms are preferred. The Quaternary nitrogen atoms can be 4 different or z. T. same Bear substituents, as well as be part of a ring system. Preferred cationic Groups are ammonium and imidazolium groups.  

Examples of such polymers are:

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Polymer JR® are commercially available. The compounds Celquat® H 100, Celquat L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - Quaternized guar derivatives, such as those under the names Cosmedia Guar® and Jaguar® are commercially available. Preferred guar derivatives are, for example Cosmedia Guar® C-261 and Jaguar® C 13-S.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dial kylaminoalkyl acrylate and methacrylate, such as with diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoalkyl methacrylate copolymers and that Vinyl pyrrolidone-methacrylamidopropyl trimethyl ammonium chloride copolymers. Sol che connections are under the names Gafquat®734, Gafquat®755 or Gafquat® HS 100 commercially available.
• - Copolymers of vinyl pyrrolidone with vinyl imidazolium methochloride as they are offered under the name Luviquat®.
• - Polymer Dimethyldiallylammoniumsalze and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the designations Mer quat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (Dimethyldiallylammonium chloride-acrylamide copolymer) commercially available Products are examples of such cationic polymers.
• - Cationically derivatized silicone oils, such as those commercially available Products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilyl amodimethicone), Dow Corning 939 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059 (Her manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quater nium-80).
• - Chitosan and its derivatives.

Particularly preferred conditioning agents are quaternized ammonium compounds at least one fat residue. Such connections are, for example, under the Trade names Incroquat® (stearyldimethylbenzylammonium chloride; INCI name:  Stearalkonium chloride; Croda GmbH) and Ammonyx® 4 (N, N-Dimethyl-N-Octadecyl- N-benzylammonium chloride; INCI name: Stearalkonium chloride; Stepan GmbH) expelled.

The conditioning agents are usually in an amount of 0.1 to 5% by weight, in particular in an amount of 1 to 3% by weight, in the wave agents according to the invention contain.

Furthermore, the agents according to the invention can contain all ingredients known for Weil agents, e.g. B .:

• - zwitterionic surfactants such as betaines and 2-alkyl-3-carboxymethyl-3- hydroxyethyl imidazolines.
• Ampholytic surfactants, such as N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acids and alkylamino acetic acids.
• Thickeners such as agar agar, guar gum, alginates, xanthan gum and cellulose Derivatives such as hydroxyethyl and methylhydroxypropyl cellulose,
• Structurants such as glucose and maleic acid,
• - Anionic, zwitterionic, amphoteric and nonionic polymers as for for example vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate Copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, Me thyl vinyl ether / maleic anhydride copolymers and their esters, uncrosslinked and with Polyols cross-linked polyacrylic acids, acrylamidopropyl trimethylam monium chloride / acrylate copolymers, octylacrylamide / methyl methacrylic lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, Polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrole don / dimethylaminoethyl methacrylate vinyl caprolactam terpolymers and ge optionally derivatized cellulose ethers and silicones.
• - solubilizers such as ethanol, isopropanol, glycerin and diethylene glycol,
• - Substances for adjusting the pH such as sodium hydroxide solution, ammonia, Am moniuncarbonate, ammonium carbamate and citric acid / sodium citrate buffer,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and plant extracts,  
• - light stabilizers,
• Complexing agents such as NTA and phosphonic acids,
• Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, Carbonates, hydrogen carbonates, guanidines and primary, secondary and tertiary Phosphates,
• Opacifiers such as latex,
• - dyes,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Pearlescent agents such as ethylene glycol mono- and distearate and fatty acid alkanolamides,
• - blowing agents such as propane-butane mixtures, N20, dimethyl ether and air.

The exposure time of the waving agents on the hair is usually 15 to 40 minutes, being the nature of the hair, the chemical already done Hair treatments, the desired degree of deformation and the size of the used mechanical deformation aid (hair roller) are other influencing factors.

The waving agents according to the invention can be formulated as ready-to-use mixtures that can be used directly by the hairdresser or end user. It has In some cases, however, proved to be advantageous or necessary if the funds in two separate preparations are formulated, which are first used by the user ready-to-use waving agents are mixed.

A second object of the present invention are therefore means that consist of two separate preparations exist. It should be noted that the first preparation is the Component (A) and the second preparation contains component (B). Both For the purposes of this invention, preparations have a pH of 6.5 to 9. According to the invention, it may be preferred that all other constituents together with component (B) is contained in the second preparation.

It may be preferred to use the agents according to the invention within the framework of a Use multi-step process for permanent shaping of human hair.  

Such a method can be characterized, for example, by the following 10 steps:

• a) washing the hair.
• b) winding the hair on curlers.
• c) Applying the waving agent according to the invention and leaving on for 20 to 60 minutes the curled hair.
• d) rinsing the wound hair with warm water.
• e) If necessary, dab the wound hair.
• f) Rinsing the wound hair with an acidic aqueous solution with a pH from 1.5 to 3.5 of a physiologically compatible inorganic and / or organic Acid.
• g) application of an aqueous oxidizing agent solution (fixation) and 5 to 15 minutes let absorb.
• h) Removing the hair curlers.
• i) Rinsing the hair with warm water
• j) drying the hair.

In a variant of the method described, after unwinding the hair (Step h) another fixation for 4 to 10 minutes with a fixative.

The methods according to the invention are subject to the use of the known ones Fixing agent no restrictions.

Common components of the fixative are oxidizing agents, e.g. As sodium bromate, potassium bromate, hydrogen peroxide, and the usual stabilizers for stabilizing aqueous hydrogen peroxide preparations. The pH of such aqueous H ₂ O ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H ₂ O ₂ , is preferably 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives usually contain the bromates in concentrations of 1 to 10 and the pH of the solutions is adjusted to 4 to 7. Fixing agents based on enzymes (peroxidases) which contain no or only small amounts of oxidizing agents, in particular H ₂ O ₂ , are also suitable.

The fixatives can be formulated as solids. They contain that Oxidizing agent then in the form of a solid, for. B. potassium or sodium bromate. First shortly before use, these agents are then mixed with water. It can also be preferred to formulate the oxidizing agent as a two-component system. The two components, one of which preferably a hydrogen peroxide solution or is an aqueous solution of another oxidizing agent and the other is the remaining Be contains ingredients, are also only mixed shortly before use.

Rinses are usually carried out with water in the process according to the invention performed, to which inorganic salts can be added. In a special Embodiment can in the intermediate rinse (rinse step d) the water dissolved salts Reduced hair swelling included, as in EP-B1-0 443 356 explicitly described.

Both the waving agent and the fixing agent can 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 as e.g. B. propane-butane mixtures, nitrogen, CO ₂ , air, N ₂ O, dimethyl ether, chlorofluorocarbon blowing agents or mixtures thereof are filled in aerosol containers with a foam valve.

A third object of the present invention is the use of the above described means for permanent deformation of human hair.  

Embodiments

All data in the following examples are given in percent by weight.

example 1

A commercially available permanent wave (Natural Styling 0 der Hans Schwarzkopf GmbH) based on thioglycolate.

(a) Pretreatment of the hair to determine the waviness and tear resistance

The determination of the corrugated stability and the check of the tear strength was carried out on 25 cm long, undamaged, medium blonde, European human hair from Kerling carried out. The hair was pretensioned with 1 g on a steel roller (V2A) of 2 mm in diameter, wetted and at 45 ° C for 30 min in a flat  Dish treated with 30 ml of waving agent. Then it was rinsed intensively with water, 10 minutes with 30 ml of a commercially available fixation (Stabilfix from Hans Schwarzkopf GmbH) fixed and rinsed again with water (25 ° C). Then the hair was removed Wrapped and determined the wet tensile strength of individual hair.

(b) Determination of wet tear strength

The wet tensile strength is determined on individual hairs and averaged out of 10 Measurements indicated. Untreated hair was also tested for comparison. The The tensile strength of the wet hair was measured using a tensile stretching device (Instron, Type 112) determined. The apparatus works on the principle of constant force or Increase in elongation.

The condition of hair can be read from the measured values. The maximum pulling force is a measure of the maximum force with which a hair is stretched can without tearing. This is used to determine the fineness-related maximum tensile force Force in relation to the length-related mass of the fiber. The stronger hair are damaged, the more fragile they become. This translates into a lesser fineness-related maximum tensile force.

The maximum stretch is a measure of the elasticity of a hair before it tears. Larger values of the maximum force stretch speak for well-groomed hair.

(c) Determination of the wave stability

The measurements were carried out in the form of individual hair tests with 12 hairs each, which, as described under point (a), were subjected to permanent wave treatment with the wave solution according to the invention or the comparison solution. The corrugation stability was determined using the following formula:

The number of waves before treatment W ₀ corresponds to the number of turns of the strand on the winder. The strands were then removed from the winder and hung up in a conditioned room at 20 ° C. and a relative air humidity of 65% for 24 h. The wave number after this treatment is included as W _t in equation (1).

The accuracy in determining the wavenumbers in this experiment is one half wave number.

evaluation

The following measured values were found:

The values of the fineness-related maximum tensile force and the maximum force elongation for the with the hair treated according to the invention E1 are closer to the values of untreated hair than in the comparison formulations. In comparison to the recipes V1 and V2 leads the inventive agent E1 to a significantly reduced one Hair damage. The comparison of the wave stabilities also shows that the mean E1 is a better hair curl than a pure sulfite wave (V1).

With the permanent wave agent E1 according to the invention, one was used in 3 comparative subjects Permanent wave treatment carried out in 10-step procedure, the result of 4 experts was judged. It got a good wave result with extremely little hair damage receive.

Claims (13)

1. Agent for permanent deformation of keratin fibers, characterized in that in an aqueous preparation with a pH of 6 to 9.5

• A) at least one water-soluble sulfite, bisulfite or hydrogen sulfite in the form of the alkali, alkaline earth or ammonium salt in an amount of 2-15% by weight, based on the total agent,
• B) at least one thio compound in an amount of 0.01-5 wt .-%, based on the whole agent, and
• C) at least one protein derivative

are included, with the proviso that the amount of component (A) is greater than the amount of component (B). 2. Means for permanent deformation of keratin fibers according to claim 1, characterized characterized in that component (B) is selected from glutathione, dithiothreitol, Cysteamine and cysteine and their physiologically acceptable salts. 3. Means for permanent deformation of keratin fibers according to claim 2, characterized characterized in that the components (B) cysteine or a cysteine salt of a is physiologically acceptable acid. 4. Means for permanent deformation of keratin fibers according to one of claims 1 to 3, characterized in that it is a quaternized as component (C) Contains protein hydrolyzate. 5. Agent for permanent deformation of keratin fibers according to one of claims 1 to 5, characterized in that it additionally contains a penetration agent and / or Contains wetting agents. 6. Agent for permanent deformation of keratin fibers according to claim 5, characterized in that the penetrant is selected from a group which is formed by urea, imidazole, 1,3-butanediol, ethoxydiglycol and the C ₂ - to C ₆ polyols. 7. Means for permanent deformation of keratin fibers according to one of claims 5 or 6, characterized in that the wetting agent is selected from the group of nonionic, anionic and cationic surfactants. 8. Means for permanent deformation of keratin fibers according to claim 7, characterized characterized in that the wetting agent is an alkyl polyglycoside. 9. Means for permanent deformation of keratin fibers according to one of claims 1 to 8, characterized in that it contains a further conditioning agent. 10. Means for permanent deformation of keratin fibers according to claim 9, characterized characterized in that the further conditioning agent is selected from the group formed from amino acids, cationic polymers and quaternary Ammonium compounds. 11. Means for permanent deformation of keratin fibers according to one of claims 1 to 10 consisting of two separate preparations to be stored, thereby characterized in that the first preparation component (A) and the second Preparation containing component (B). 12. Means for permanent deformation of keratin fibers according to claim 11, characterized characterized in that all other components together with component (B) in the second preparation are included. 13. Use of an agent of claims 1 to 12 for permanent deformation keratin fibers.