DE10224248A1 - New di-2-((4-acetamido- and -amino-2-nitrophenyl)amino)-ethyl disulfide and known dye thiol and disulfide compounds are used with enzyme of protein disulfide isomerase type in cosmetic for treating keratinous fibers, especially human hair - Google Patents

Abstract

Di-2-((4-acetamido-2-nitrophenyl)amino)-ethyl disulfide (IV) and di-2-((4-amino-2-nitrophenyl)amino)-ethyl disulfide (V) are new. Di-2-((4-acetamido-2-nitrophenyl)amino)-ethyl disulfide of formula (IV) and di-2-((4-amino-2-nitrophenyl)amino)-ethyl disulfide of formula (V) are new. An Independent claim is also included for cosmetic agent for treating keratinous fibers, especially human hair, which contains enzyme(s) of the protein disulfide isomerase type (EC 5.3.4.1) and is free from carbohydrate derivatives with disulfide (-S-S-) or thiol (-SH) group(s).

Description

The invention relates to a method for the enzymatic treatment of keratin fibers, especially human hair, with cosmetic Agents that contain the enzyme protein disulfide isomerase, as well as in enzyme-containing agents used in this process and its use for Care of fibers containing keratin and / or in combination with a permanent one Deformation of the fibers.

The cleaning and care of the hair is an important part of human Personal hygiene. Both cleaning the hair with shampoos as well decorative design of the hairstyle, for example by dyeing or perming, are interventions that change the natural structure and properties of the hair. influence. For example, following such treatment the wet and dry combability, hold, fullness, shine and tactility of the hair to be unsatisfactory. In addition, the hair is damaged Environmental influences such as UV, IR radiation and heat, e.g. B. by blow drying of the hair.

It is therefore necessary to maintain and restore the aforementioned properties It has long been customary to subject the hair to a special after-treatment. The hair, usually in the form of a conditioner, is treated with special Active ingredients, for example quaternary ammonium salts or special Polymers, treated. Depending on the formulation, combability, hold, Hair fullness, shine and feel improved. For the temporary influence of the Hair volume is the use of polyaminoglucoses as in EP-A-0412745 and US-A-5,523,078, of cellulose as in JP-A-04124121 and EP-A-0823252 as well Alkyl cellulose in WO-A-97/38673, US-A-5,534,247 and WO-A-94/06410 described. Furthermore, you will also find smaller carbohydrate components such as Glucose in WO-A-95/00104, maltose in WO-A-95/00104 and lactose in DE-A-196 10 458 Application. When applying such rinses, however, only remains a relatively small proportion of the active ingredients at their place of action. The majority will rinsed off immediately or by washing your hair later or mechanically Stress, such as B. combing, detached from the hair surface.

The treatment of keratinous material such. B. wool with protein Disulfide isomerase is described in EP-B1-276 547 and EP-B1-276 781 described.

US-A-3,619,114 teaches the permanent modification of keratinous substrates by copolymerization with vinyl monomers in the presence of radicals Catalysts and subsequent treatment with aqueous ammoniacal Kupferhydroxydlösungen. Due to the toxicity of the compounds used, however, the application is limited to inanimate keratin fibers. US A-2,615,782 teaches the modification of keratinous fibers by knotting Disulfide bridges between hair and active substance. Another method of Fixation of connections that serve the permanent deformation of hair and which is particularly aimed at permanent wave processes, is the use of so-called Colorful salt derivatives, as in DE-A-37 35 086, DE-A-41 09 869 and EP-A-0246151 described. US-A-3,415,606 teaches the use of reactive dyes have a long-term effect on the hair.

It is therefore of urgent interest to be protective, uplifting and Restructuring active ingredients preferably permanently fixed to the hair and at the same time a burden on the environment and a health impairment to avoid the user.

The object of the present invention is to provide a means and a method for To provide treatment of fibers containing keratin, with the help of which a Let the fiber be cared for and restructured. By the The inventive method is a care of the fiber and optionally a allows simultaneous deformation of the fiber.

A first subject of the invention is therefore a cosmetic agent Treatment of keratin fibers, especially human hair, the contains at least one enzyme of the protein disulfide isomerase type (EC 5.3.4.1) and is free of carbohydrate derivatives with at least one disulfide group (-S-S-) or thiol group (-SH).

Enzymes are named after the official Enzyme Nomenclature of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (IUBMB) classified with EC number (Enzyme Conimission). A complete List of characterized enzymes from the enzyme classes according to IUBMB is in the SwissProt database can be found at http: / / www.expasy.ch.

Enzymes from the enzyme class EC 5.3.4.1 (official name: protein Disulfide isomerase) preferentially catalyze the isomerization of intermolecular ones and intramolecular disulfide bonds in proteins.

For example, protein disulfide isomerases made from beef liver, or E. coli or enzymes with disulfide isomerase activity which are accessible by recombination, such as in the publication US-B1-6,387,683, to which reference is expressly made here is taken.

Aqueous, alcoholic and oily are particularly suitable according to the invention Preparations and their mixtures. Aqueous preparations are preferred. In the context of the invention, such preparations are aqueous preparations understood that at least 10 wt .-% water, based on the total agent, contain. It can be, for example, solutions, dispersions, emulsions (Water in oil emulsions, oil in water emulsions and multiple emulsions and PIT emulsions). Furthermore, it is still possible formulate agents according to the invention as a two-phase or multi-phase system, in which the separated phases by mechanical movement shortly before Application to be mixed to form a metastable dispersion. The Dispersion separates a few seconds or minutes after Mixing process again in the separate phases.

The pH of the preparations according to the invention is generally 4 to 9, preferably 6 to 8 and particularly preferably 7.3 to 7.7. In a special Embodiment for an acidic perm, the pH is less than pH 7, with Trend in the slightly acidic range until it reaches about pH 6. In a special Embodiment for a basic perm is the pH of the Agent according to the invention greater than pH 8 and is preferably in the range up to about pH 10.

Bases such as ammonia and organic are used to adjust the pH Amine compounds such as B. monoethanolamine, or hydroxides of the alkali metals as well as acids such. B. phosphoric acid, hydrochloric acid or organic acids such as z. B. acetic acid or edible acids such as citric acid, tartaric acid or malic acid, use.

The enzyme is preferably in an amount of 0.1 to 2000 units of enzyme, preferably from 500 to 1500 units of enzyme in the agent according to the invention contain. U (unit) is the amount of enzyme, the 1 unit of unfolded ribonuclease (RNase) fold again within one minute at pH 7.5 and 30 ° C (reactivate) can. To measure the. RNase activity becomes reduced RNase A from bovine with protein disulfide isomerase in the presence of cCMP (cyclic Cytidine monophosphate) and glutathione treated with PDI. The split of the cCMP by reactivated RNase A using a spectrometer at a wavelength of 284 nm tracked. In this way, the reactivation of RNase A is complete Protein disulfide isomerase, for example by an RNase assay from TaKaRa Shuzo Co. Ltd., Biomedical Group, Japan. A This measurement method is also described in Goldberger, R.F., Epstein, C. J., Anfinsen, C. B. (1964) J. Biol. Chem., 239, 1406; Lambert, N. and Freedman, R. B. (1983), Biochem. J., 213, 225; Hillson, D.A., Lambert, N., Freedman, R. B. (1984), Methods in Enzymology 107, 281; Tang, J.G., Wang, C.C., Tsou, C.L. (1988) Biochem. 1, 255, 451 and Gething, M.J. and Sambrook, J. (1992), Nature 355, 33.

Compounds preferably serve as substrates for the protein disulfide isomerase, for example proteins that carry disulfide bridges or free thiol groups. The The presence of free thiol groups on the substrate promotes the course of the isomerization. It is therefore preferred according to the invention to use the protein Disulfide isomerase on the hair in the presence of a keratin-reducing To use reducing agent. As a preferred reducing agent contain the agents according to the invention thioglycolic acid, thiolactic acid, thio malic acid, DL- Dithiothreitol, glutathione, mercaptoethanesulfonic acid and their salts and esters, Cysteamine, cysteine and salts of sulphurous acid. DL-dithiothreitol or Thioglycolic acid are particularly preferred.

The keratin-reducing agents are preferred in the agent according to the invention in an amount of 0.0001 to 0.5% by weight, based on the total agent, contain.

In one embodiment, the agents according to the invention contain at least a complexing agent. EDTA, for example, are suitable as complexing agents, NTA, β-alaninediacetic acid, polyphosphonic acids, polyphosphates as well organic acids such as B. citric acid. EDTA or its physiological compatible salt is a preferred complexing agent in the sense of the present Invention.

In another embodiment, the agents according to the invention contain at least one surfactant, in principle both anionic and zwitterionic, Ampholytic, nonionic and cationic surfactants are suitable. In many In some cases, however, it has proven advantageous to use anionic, select zwitterionic or nonionic surfactants.

• - lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x- SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354,
• - Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344,
• - Ester der Weinsäure und Citronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2 bis 15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

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, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts 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,
• - Monosulfonic acid and dialkyl sulfosuccinates with 8 to 18 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 18 carbon 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 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• sulfated 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 bonds according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2 to 15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 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 ,

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-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 CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C _8-18 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. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

• - Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - C_12-22-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - C_8-22-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga,
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• - Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester
• - Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide.

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

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

Examples of those in the hair treatment agents according to the invention Cationic surfactants that can be used are, in particular, quaternary ammonium compounds. Ammonium halides such as alkyltrimethylammonium chlorides are preferred. Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further according to the invention usable cationic surfactants are the quaternized protein hydrolyzates.

Cationic silicone oils such as for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxyl-amino-modified silicone, 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).

Alkylamidoamines, especially fatty acid amidoamines like that under the Name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out in addition to a good conditioning effect, especially due to its good biological Degradability.

Quaternary ester compounds are also very biodegradable, So-called "esterquats", such as those sold under the Stepantex® trademark Methylhydroxyalkyldialkoyloxyalkylammonium.

An example of a quaternary that can be used as a cationic surfactant Sugar derivative is the commercial product Glucquat®100, according to the CTFA nomenclature "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds with alkyl groups used as surfactants can act in each case uniform substances. However, it is usually preferred in the manufacture of these substances from native plant or animal Raw materials go out, so that you can mix substances with different, from receives respective raw material dependent alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide of fatty alcohols or derivatives of these adducts both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. Under "normal" Homolog distribution is understood to be mixtures of homologs that one in the implementation of fatty alcohol and alkylene oxide using Alkali metals, alkali metal hydroxides or alkali metal alcoholates as Receives catalysts. On the other hand, narrow homolog distributions are obtained if for example hydrotalcites, alkaline earth metal salts of ether carboxylic acids, Alkaline earth metal oxides, hydroxides or alcoholates can be used as catalysts.

The use of products with a narrow homolog distribution can be preferred.

The surfactants in the agents according to the invention are usually in amounts of 0.1 to 65 wt .-%, preferably in amounts of 2 to 50 wt .-% and whole particularly preferably in amounts of 8 to 20% by weight, based on the total Means included. Nonionic surfactants are preferred in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 5% by weight.

In a further embodiment of the present invention, the agents in Formulated a thickened solution. For this purpose, the means with at least one thickener such as agar agar, guar gum, alginates, Xanthan gum, gum arabic, karaya gum, locust bean gum, Flaxseed 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 as B. polyvinyl alcohol or Thickened polyacrylic acid polymers.

Furthermore, the preparations used according to the invention can additionally contain at least one oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances and their mixtures with solid Paraffins and waxes. According to the invention, such are insoluble in water Substances defined whose solubility in water at 20 ° C is less than 0.1% by weight is. The melting point of the individual oil or fat components lies preferably below about 40 ° C. Oil and fat components, which at Room temperature, d. H. are liquid below 25 ° C, can according to the invention be particularly preferred. When using several oil and fat components as well as solid paraffins and waxes, as a rule, however sufficient if the mixture of oil and fat components as well as Paraffins and waxes meet these conditions.

A preferred group of oil components are vegetable oils. examples for such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, Orange oil, avocado oil, wheat germ oil, peach seed oil and the liquid parts of the Coconut oil.

However, other triglyceride oils such as the liquid portions of the are also suitable Beef tallow and synthetic triglyceride oils.

Another particularly preferred group according to the invention as an oil component usable compounds are liquid paraffin oils and synthetic Hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 C Atoms, in particular 12 to 24 carbon atoms, such as di-n-octyl ether, Di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-ndodecyl ether, n-hexyl noctyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-ndodecyl ether and n-hexyl-n-undecyl ether as well as di-tert-butyl ether, Di-isopentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The available as commercial products Compounds 1,3-di- (2-ethylhexyl) cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE) can be preferred.

Oil components which can likewise be used according to the invention are fatty acid and Fettalkoholester. The monoesters of fatty acids with alcohols with 3 are preferred up to 24 carbon atoms. This group of substances are the products of Esterification of fatty acids with 8 to 24 carbon atoms such as Caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, Isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, Elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the z. B. in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's Oxosynthesis or the dimerization of unsaturated fatty acids occur with Alcohols such as isopropyl alcohol, capro alcohol, caprylic alcohol, 2- Ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, Cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, Elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, the z. B. at the High pressure hydrogenation of technical methyl esters based on fats and Oils or aldehydes from Roelen's oxosynthesis and as Monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, particular preference is given to isopropyl myristate, isononanoic acid C16-18 alkyl ester (Cetiol® SN), stearic acid 2-ethylhexyl ester (Cetiol® 868), Cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate / caprylate and n- Butyl stearate.

Dicarboxylic acid esters such as di-n-butyl adipate and di- (2-ethylhexyl) - adipate, di- (2-ethylhexyl) succinate and di-isotridecylacelate as well as diol esters such as Ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2- ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, Butanediol di-isostearate and neopentyl glycol di-capylate according to the invention usable oil components, as well as complex esters such. B. that Diacetylglycerinmonostearat.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used according to the invention acting oil components are used. The fatty alcohols can be saturated or unsaturated and linear or branched. Can be used in the sense of the invention are, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, Dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, Stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, Arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, this list exemplary and non-limiting character. The fatty alcohols however, preferably derived from natural fatty acids, usually from extraction from the esters of fatty acids by reduction can be assumed. Such can also be used according to the invention Fatty alcohol cuts by reducing naturally occurring triglycerides such as Beef tallow, palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from their transesterification products with appropriate alcohols resulting fatty acid esters are generated, and thus a mixture of represent different fatty alcohols.

The agents used according to the invention can additionally be conventional Care substance included. This care substance is preferably selected from cationic polymers and silicones.

A first group of cationic polymers are the so-called "temporary cationic "polymers. These polymers usually contain one Amino group, which at certain pH values as a quaternary ammonium group and is therefore cationic.

However, the cationic polymers are permanently cationic Polymers preferred. According to the invention, such are considered to be “permanently cationic” Polymers that are cationic regardless of the pH of the agent Have group. These are usually polymers that are quaternary Contain nitrogen atom, for example in the form of an ammonium group.

• - quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat® und Polymer JR® im Handel erhältlich sind. Die Verbindungen Celquat® H 100, Celquat® L 200 und Polymer JR®400 sind bevorzugte quaternierte Cellulose-Derivate,
• - Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80),
• - Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia®Guar und Jaguar® vertriebenen Produkte,
• - Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,
• - Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat®734 und Gafquat®755 im Handel erhältlich,
• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat® FC 370, FC 550, FC 905 und HM 552 angeboten werden.
• - quaternierter Polyvinylalkohol,
• - sowie die unter den Bezeichnungen
• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 und
• - Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

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,
• Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, 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),
• - Cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia®Guar and Jaguar®,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755,
• - Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as are offered under the names Luviquat® FC 370, FC 550, FC 905 and HM 552.
• - quaternized polyvinyl alcohol,
• - as well as under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Can also be used as cationic polymers under the Designations Polyquaternium-24 (commercial product e.g. Quatrisoft® LM 200), Polyquaternium-32, Polyquaternium-35 and Polyquaternium-37 (commercial products z. B. Salcare® SC 92 and Salcare®SC 95) known polymers. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone as they are as commercial products Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat®8155 and Luviquat® MS 370 are available.

Cationic polymers preferred according to the invention are quaternized cellulose Derivatives, polymeric dimethyldiallylammonium salts, polyquaternium-27 and their Copolymers and polymers of the type polyquaternium-2. Cationic cellulose Derivatives, especially the commercial product Polymer®JR 400, and polymers from Type Polyquaternium-2, especially the commercial product Mirapol®A-15, are whole particularly preferred cationic polymers.

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

Ampho-polymers are also suitable as a care substance in combination with or as an alternative to cationic polymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO or -SO ₃ groups, and summarize those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its 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 trimethylammonium chloride) and optionally other ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the state of the art cited there. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention.

Care substances that can be used according to the invention are furthermore silicone oils and silicone Gums, especially dialkyl and alkylarylsiloxanes, such as Dimethylpolysiloxane and methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues. Examples of such silicones are those from Dow Corning below products sold under the names DC 190, DC 200 and DC 1401 as well as the commercial products DC 344 and DC 345 from Dow Corning, Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 Emulsion (containing a hydroxylamino modified silicone, also known as Amodimethicone is called), SM-2059 (manufacturer: General Electric), SLM- 55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80) and that Commercial product Fancorsil® LIM-1. A suitable anionic silicone oil is that Product Dow Corning®1784.

Examples of the conditioning and in the agents according to the invention Caring surfactants that can be used are, in particular quaternary ammonium compounds. Ammonium halides are preferred, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, Distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Farther the very readily biodegradable quaternary ester compounds, So-called "esterquats", such as those under the trademarks Dehyquart® and Stepantex® Methyl-hydroxyalkyl-dialkoyloxyalkylammonium methosulfates can be used.

Alkylamidoamines, especially fatty acid amidoamines like that under the Name Tego Amid®S 18 available stearylamidopropyldimethylamine in addition to a good conditioning effect, especially through its good biodegradability.

• - heterocyclische Verbindungen wie Imidazol, Pyrrolidin, Piperidin, Dioxolan, Dioxan, Morpholin und Piperazin sowie Derivate dieser Verbindungen wie beispielsweise die C_1-4-Alkyl-Derivate, _1-4-Hydroxyalkyl-Derivate und C_1-4- Aminoalkyl-Derivate. Bevorzugte Substituenten, die sowohl an Kohlenstoffatomen als auch an Stickstoffatomen der heterocyclischen Ringsysteme positioniert sein können, sind Methyl-, Ethyl-, β-Hydroxyethyl- und β-Aminoethyl-Gruppen. Erfindungsgemäß bevorzugte Derivate heterocyclischer Verbindungen sind beispielsweise 1-Methylimidazol, 2- Methylimidazol, 4(5)-Methylimidazol, 1,2-Dimethylimidazol, 2-Ethylimidazol, 2- Isopropylimidazol, N-Methylpyrrolidon, 1-Methylpiperidin, 4-Methylpiperidin, 2- Ethylpiperidin, 4-Methylmorpholin, 4-(2-Hydroxyethyl)morpholin, 1- Ethylpiperazin, 1-(2-Hydroxyethyl)piperazin, 1-(2-Aminoethyl)piperazin. Weiterhin erfindungsgemäß bevorzugte Imidazolderivate sind Biotin, Hydantoin und Benzimidazol. Ganz besonders bevorzugt ist das Imidazol.
• - Aminosäuren wie insbesondere Arginin, Citrullin, Histidin, Ornithin und Lysin. Die Aminosäuren können sowohl als freie Aminosäure als auch als Salze, z. B. als Hydrochloride, eingesetzt werden. Weiterhin haben sich auch Oligopeptide aus durchschnittlich 2-3 Aminosäuren, die einen hohen Anteil (> 50%, insbesondere > 70%) an den genannten Aminosäuren haben, als erfindungsgemäß einsetzbar erwiesen. Erfindungsgemäß besonders bevorzugt sind Arginin sowie dessen Salze und argininreiche Oligopeptide.
• - Diole wie beispielsweise 2-Ethyl-1,3-hexandiol, 1,3-Butandiol, 1,4-Butandiol, 1,2-Propandiol, 1,3-Propandiol, Neopentylglykol und Ethylenglykol. 1,3-Diole, insbesondere 2-Ethyl-1,3-hexandiol und 1,3-Butandiol, haben sich als besonders gut geeignet erwiesen.

Furthermore, it may be preferred to add corrugation-strengthening components to the agent according to the invention, such as:

• - Heterocyclic compounds such as imidazole, pyrrolidine, piperidine, dioxolane, dioxane, morpholine and piperazine as well as derivatives of these compounds such as the C _1-4 -alkyl derivatives, _1-4 -hydroxyalkyl derivatives and C _1-4 - 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. 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 preferred according to the invention are biotin, hydantoin and benzimidazole. Imidazole is very particularly preferred.
• - Amino acids such as arginine, citrulline, histidine, ornithine and lysine in particular. The amino acids can be used both as free amino acids and as salts, e.g. B. be used as hydrochlorides. Furthermore, oligopeptides of an average of 2-3 amino acids, which have a high proportion (> 50%, in particular> 70%) of the amino acids mentioned, have also proven to be usable according to the invention. Arginine and its salts and arginine-rich oligopeptides are particularly preferred according to the invention.
• - Diols such as 2-ethyl-1,3-hexanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol and ethylene glycol. 1,3-diols, especially 2-ethyl-1,3-hexanediol and 1,3-butanediol, have proven to be particularly suitable.

With regard to more detailed information on such waving-strengthening components is referred to the publications DE-OS 44 36 065 and EP-B1-363 057 on the content of which is expressly referred to.

The corrugation-strengthening compounds can in the invention Agents in amounts of 0.5 to 5% by weight, based on the total agent, be included. Amounts from 1 to 4% by weight, in the case of the diols from 0.5-3% by weight %, have proven to be sufficient, which is why these amounts are special are preferred.

In a particularly preferred embodiment, the agents according to the invention contain at least one care substance which contains a thiol group or a disulfide group. Such care substances have a substrate activity for the protein disulfide isomerase. It may be preferred to use the care substance in an amount of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.1 to 2% by weight, based on the total agent. use. Care substances which are selected from compounds of the formula I are preferably used,

R ¹ -Y ¹ -G ¹ -XG ² -Y ² -R ² (I)

wherein,
X represents a thio group (-S-) or a disulfide group (-SS-)
G ¹ , G ² independently of one another represent a direct bond, a C ₁ -C ₁₀ alkylene group, an arylene group, an arylene C ₁ -C ₁₀ alkylene group, G ² meaning a direct bond if X is a Thio group stands.
Y ¹ , Y ² independently of one another represent a direct bond, an azo group, a group -NH-C (O) -, a group -OC (O) -, a thio group (-S-) or an oxy group (-O- ), and Y ² means a direct bond when X represents a thio group,
R ¹ , R ² represent a hair care component, where R ¹ and R ^{2 may be the} same or different and the radical R ^{2 represents} a hydrogen atom if X represents a thio group.

In a preferred embodiment, X represents a disulfide group.

Preferred C ₁ -C ₁₀ alkylene groups are the methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, pentylene, hexylene, cyclohexylene, n-octylene and n- decylene. Examples of arylene groups according to the invention are the phenylene, biphenylene or naphthylene group, the phenylene group is preferred. Arylene-C ₁ -C ₁₀ -alkylene groups according to the invention are, for example, the benzylidene, phenylene ethylene, phenylene propylene, phenylene butylene, phenylene hexylene or naphthylene ethylene group.

• - linearen und/oder verzweigten und gesättigten und/oder ungesättigten Fettsäuren, bevorzugt C₂-C₃₀- Fettsäuren, besonders bevorzugt C₄-C₂₄ Fettsäuren, am meisten bevorzugt C₆-C₂₂-Fettsäuren und/oder deren physiologisch verträglichen Salzen; Weitere Beispiele leiten sich ab von den Carbonsäuren wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, Valeriansäure, Isovaleriansäure, Pivalinsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Glycerinsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Propiolsäure, Crotonsäure, Isocrotonsäure, Elaidinsäure, Maleinsäure, Fumarsäure, Muconsäure, Citraconsäure, Mesaconsäure, Camphersäure, Benzoesäure, o,m,p-Phthalsäure, Naphthoesäure, Toluoylsäure, Hydratropasäure, Atropasäure, Zimtsäure, Isonicotinsäure, Nicotinsäure, Bicarbaminsäure, 4,4'- Dicyano-6,6'-binicotinsäure, 8-Carbamoyloctansäure, 1,2,4- Pentantricarbonsäure, 2-Pyrrolcarbonsäure, 1,2,4,6,7- Napthalinpentaessigsäure, Malonaldehydsäure, 4-Hydroxy-phthalamidsäure, 1-Pyrazolcarbonsäure, Gallussäure oder Propantricarbonsäure, sowie von den Dicarbonsäuren ausgewählt aus der Gruppe, die gebildet wird durch Verbindungen der allgemeinen Formel (II),
  
  
  in der Z steht für eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit 4 bis 12 Kohlenstoffatomen, n für eine Zahl von 4 bis 12 sowie eine der beiden Gruppen X und Y für eine COOH-Gruppe und die andere für Wasserstoff oder einen Methyl- oder Ethylrest, Dicarbonsäuren der allgemeinen Formel (II), die zusätzlich noch 1 bis 3 Methyl- oder Ethylsubstituenten am Cyclohexenring tragen sowie Dicarbonsäuren, die aus den Dicarbonsäuren gemäß Formel (II) formal durch Anlagerung eines Moleküls Wasser an die Doppelbindung im Cyclohexenring entstehen;
• - linearen und/oder verzweigten und gesättigten und/oder ungesättigten Alkoholen, bevorzugt C₂-C₃₀- Alkoholen, besonders bevorzugt C₄-C₂₄- Alkoholen, am meisten bevorzugt C₆-C₂₂- Alkoholen; wie beispielsweise Ethanol, Butanol, Hexanol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Linoleylalkohol;
• - Alkylamidoaminen, z. B. Tego Amid® S 18 (Stearylamidopropyldimethylamin);
• - Aminosäuren und ihren Derivaten, z. B. Aminosäureamide, insbesondere Di-, Tri- oder Tetra-Peptide, Aminosäureester und/oder phosphorylierte Aminosäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Alanin, Arginin, Cystein, Glutamin, Glycin, Histidin, Lysin, Leucin, Ornithin, Isoleucin, Serin, Tyrosin, Tryptophan, Valin und Phenylalanin;
• - Peptiden, insbesondere Oligopeptiden, wie z. B. Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, wobei Peptide mit einer Masse M < 1000 besonders bevorzugt sind;
• - Polyhydroxyverbindungen, die keine Kohlenhydratderivate darstellen; hierbei sind insbesondere zu nennen;
• - Polyole, wie z. B. Glucamine, Glycerin, Mono- oder Diglyceride, 2-Ethyl- 1,3-hexandiol, 2-Hydroxymethylpropantriol, Glycole wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Propylenglykol, Dipropylenglykol, 1,3- Butandiol;
• - Polyhydroxysäuren, wie z. B. Pentahydroxyhexansäure, Tetrahydroxypentansäure und/oder deren Derivate, wie z. B. Ether, Ester und/oder Amide, z. B. Pentahydroxyhexansäureamid und/oder deren physiologisch verträglichen Salzen; weitere Beispiele: Zitronensäure, Äpfelsäure oder Weinsäure;
• - Silikone, wie z. B. Cyclomethicone (Octamethylcyclotetrasiloxan, Decamethylcyclopentasiloxan, Dodecamethylcyclohexasiloxan), Hexamethyldisiloxan, Dimethicon-Copolymere, Polysiloxane sowie quaternierte Polysiloxane;
• - quaternierte Ammoniumverbindungen, hierbei sind insbesondere hervorzuheben:
• - Esterquats und/oder deren Derivate, z. B. Halogenide, Methylsulfate, wobei unter Esterquats quaternierte Estersalze von Fettsäuren z. B. mit Triethanolamin, mit Diethanolalkylaminen oder mit 1,2- Dihydroxypropyldialkylaminen verstanden werden; es kann bevorzugt sein, quaternierte Estersalze von linear und/oder verzweigten aliphatischen gesättigten und/oder ungesättigten C₁-C₂₀-Fettsäuren mit den o. g. Alkanolaminen einzusetzen;
• - Ammoniumhalogenide, insbesondere Chloride und Bromide, wie Alkyltrimethylammoniumchloride, Dialkyldimethylammoniumchloride und Trialkylmethylammoniumchloride, z. B. Cetyltrimethylammoniumchlorid, Stearyltrimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Lauryldimethylammoniumchlorid, Lauryldimethylbenzylammoniumchlorid und Tricetylmethylammoniumchlorid;
• - Pantolacton;
• - Panthenol und/oder dessen Derivate;
• - weitere Vitamine, wie z. B. Vitamin B3, B6, C und/oder E und/oder deren Derivate;
• - Hydroxysäuren, wie z. B. α-, β-Hydroxyfettsäuren bzw. Ketofettsäuren und/oder deren physiologisch verträglichen Salzen; wie beispielsweise Salicylsäure oder Milchsäure, Glyoxylsäure, Glycolsäure.

The hair care component of the substituents R ¹ and R ² according to formula I is preferably derived from:

• linear and / or branched and saturated and / or unsaturated fatty acids, preferably C ₂ -C ₃₀ fatty acids, particularly preferably C ₄ -C ₂₄ fatty acids, most preferably C ₆ -C ₂₂ fatty acids and / or their physiologically tolerable salts; Further examples are derived from the carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, isocrotic acid, sebacotonic acid, sebacotonic acid, sebaconic acid , Elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid-4,4'-, 6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid, and of the dicarboxylic acids selected from the group formed by compounds of the general a formula (II),
  
  
  in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (II) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (II) by addition of a molecule of water to the double bond in the cyclohexene ring;
• linear and / or branched and saturated and / or unsaturated alcohols, preferably C ₂ -C ₃₀ alcohols, particularly preferably C ₄ -C ₂₄ alcohols, most preferably C ₆ -C ₂₂ alcohols; such as ethanol, butanol, hexanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol;
• Alkylamidoamines, e.g. B. Tego Amid® S 18 (stearylamidopropyldimethylamine);
• - Amino acids and their derivatives, e.g. B. amino acid amides, especially di-, tri- or tetra-peptides, amino acid esters and / or phosphorylated amino acids and / or their physiologically tolerable salts; such as alanine, arginine, cysteine, glutamine, glycine, histidine, lysine, leucine, ornithine, isoleucine, serine, tyrosine, tryptophan, valine and phenylalanine;
• - Peptides, especially oligopeptides, such as. B. protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, peptides with a mass M <1000 being particularly preferred;
• - polyhydroxy compounds that are not carbohydrate derivatives; here are to be mentioned in particular;
• - Polyols, such as B. glucamines, glycerol, mono- or diglycerides, 2-ethyl-1,3-hexanediol, 2-hydroxymethylpropane triol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol;
• - Polyhydroxy acids, such as. B. pentahydroxyhexanoic acid, tetrahydroxypentanoic acid and / or their derivatives, such as. B. ethers, esters and / or amides, e.g. B. pentahydroxyhexanoic acid amide and / or its physiologically tolerable salts; further examples: citric acid, malic acid or tartaric acid;
• - Silicones, such as B. cyclomethicones (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane), hexamethyldisiloxane, dimethicone copolymers, polysiloxanes and quaternized polysiloxanes;
• quaternized ammonium compounds, in particular the following should be emphasized:
• - Esterquats and / or their derivatives, e.g. B. halides, methyl sulfates, wherein quaternized ester salts of fatty acids z. B. with triethanolamine, with diethanolalkylamines or with 1,2-dihydroxypropyldialkylamines; it can be preferred to use quaternized ester salts of linear and / or branched aliphatic saturated and / or unsaturated C ₁ -C ₂₀ fatty acids with the abovementioned alkanolamines;
• - 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;
• - pantolactone;
• - panthenol and / or its derivatives;
• - Other vitamins, such as B. Vitamin B3, B6, C and / or E and / or their derivatives;
• - Hydroxy acids, such as. B. α-, β-hydroxy fatty acids or keto fatty acids and / or their physiologically tolerable salts; such as salicylic acid or lactic acid, glyoxylic acid, glycolic acid.

In a further embodiment, the agents according to the invention contain at least one substantive dye.

Suitable conventional substantive dyes are nitro dyes (such as for example nitrophenylenediamines or nitroaminophenols), azo dyes, Anthraquinone dyes, indophenols or cationic substantive dyes.

Preferred nitro dyes are selected from 4-amino-1-nitrobenzene, 2-amino-1- nitrobenzene, 1,4-diamino-2-nitrobenzene, 4-acetylamino-1-amino-2-nitrobenzene, 1,2- Diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 3-amino-6-methylamino 2-nitro-pyridine (aza red), picramic acid, 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 1- (2- Hydroxyethyl) amino-2-nitro-benzene (HC Yellow No. 2), 1- (2-hydroxyethyl) amino-2- (2-hydroxyethyl) oxy-4-nitro-benzene (HC Yellow No. 4), 1-amino-2- (2- hydroxyethyl) amino-5-nitro-benzene (HC Yellow No. 5), 1- (2,3- dihydroxypropyl) amino-4-trifluoromethyl-2-nitro-benzene (HC Yellow No. 6), 1- (2- Hydroxyethyl) amino-4-chloro-2-nitro-benzene (HC Yellow No. 12), 1-amino-2-nitro-4- [bis (2-hydroxyethyl)] amino-benzene (HC Red No. 13), 4-chloro-2,5-bis [(2,3- dihydroxypropyl) amino] -1-nitro-benzene (HC Red No. 11), 1-amino-5-chloro-4- (2, 3- dihydroxypropyl) amino-benzene (HC Red No. 10), 1-amino-2-nitro-4- (2- hydroxyethyl) amino-benzene (HC Red No. 7), 2-chloro-5-nitro-N- (2-hydroxyethyl) - 1,4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-2-nitrodiphenylamine (HC Red No. 1), 2-nitro-4'-hydroxydiphenylamine (HC Orange No. 1), 1-amino-3-methyl-4- (2-hydroxyethyl) amino-6- nitrobenzene (HC Violet No. 1), 2- (2-hydroxyethyl) amino-5- (bis (2- hydroxyethyl)) amino-1-nitro-benzene (HC.Blue No. 2), 1- (2-hydroxyethyl) amino-2- nitro-4-N-ethyl-N- (2-hydroxyethyl) amino-benzene (HC Blue No. 12), 4-amino-3,5- dinitro-benzoic acid, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 2- (4'-amino-2'- nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4- nitrophenol, 4-amino-4'-nitrostilbene-2,2'-disulfonic acid, 4'-amino-4- nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1- Amino-4-nitro-2- (2'-nitrobenzylidenamino) benzene, 2- [2- (diethylamino) ethylamino] - 5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6- nitrobenzo-1, 3-dioxole, 2-amino-6-nitrobenzothiazole, 4- (3-hydroxypropyl) amino-3- nitro-phenol (HC Red BN), 2-amino-4,6-dinitrophenol, 3-nitro-4- (2-hydroxyethyl) - aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 2-amino-6-chloro-4- nitrophenol, 2-chloro-6-ethylamino-4-nitro-phenol, 1- (2-hydroxyethyl) amino-4- methyl-2-nitrobenzene, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline and 4-ethylamino-3- nitrobenzoic acid.

Preferred anthraquinone dyes are selected from 1 - [(3-aminopropyl) amino] - anthraquinone (HC Red No. 7), 2 - [(2-aminoethyl) amino] anthraquinone (HC Orange No. 5), 1,4,5,8-tetraamino-anthraquinone (Disperse Blue 1), 1 - [(2- Hydroxyethyl) amino] -4-methylamino-anthraquinone (Disperse Blue 3), 1,4 - [(2- Hydroxyethyl) amino] -5,8-dihydroxyanthraquinone (Disperse Blue 7), 1,4-diamino- 2-methoxy-anthraquinone (Disperse Red 11), 1-amino-4-hydroxy-anthraquinone (Disperse Red 15), 1,4-diamino-anthraquinone (Disperse Violet 1), 1-Amino-4- methylamino-anthraquinone (Disperse Violet 4) and 1-amino-4-isopropylaminoanthraquinone (Disperse Violet 15).

Preferred azo dyes are selected from 4-arino-4 '- [bis (2- hydroxyethyl)] amino-azobenzene (Disperse Black 9), 4-amino-4'-nitro-azobenzene (Disperse Orange 3), 3-hydroxy-4 - [(2-hydroxy-naphth-1-yl) azo) -7-nitronaphthalene 1-sulfonic acid-chromium complex (Acid Black 52), 1-amino-2- (3'-nitrophenylazo) -7- phenylazo-8-naphthol-3,6-disulfonic acid (Acid blue No. 29), 1-amino-2- (2'-hydroxy- 4'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid (Palatinchrome green), 1-amino- 2- (3'-chloro-2'-hydroxy-5'-nitrophenylazo) -8-naphthol-3,6-disulfonic acid (gallion), 8- Amino-1-hydrQxy-2- (phenylazo) -naphthalene-3,6-disulfonic acid and diamino-3 ', 5'- dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4).

• a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
• b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
• c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908, auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Cationic direct dyes can also be present in the agent according to the invention. Are particularly preferred

• a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and
• c) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, to which reference is expressly made here, in claims 6 to 11.

Preferred cationic direct dyes of group (c) are in particular the following compounds:

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are special prefers. The cationic direct dyes, which under the Trademarks Arianor® are sold, are special according to the invention preferred representative.

In particular, cationic direct dyes can be used in the Contain agents according to the invention, which are selected from N- [4 - [[4- (Diethylamino) phenyl] [4- (ethylamino) naphth-1-yl] methylene] -2,5-cyclohexadiene-1- yliden] -N-ethyl-ethaniminium chloride (Basic Blue No. 7), N- {4 - [(4- (Dimethylamino) phenyl) 4- (phenylamino) -1-naphthalenyl] methylene} -2,5- cyclohexadien-1-ylidenes] -N-methylmethaniminium chloride (Basic Blue 26), 4 - [(4- aminophenyl) (4-imino-2,5-cyclohexadien-1-ylidene) methyl] -2-methyl-aniline hydrochloride (Basic Violet 14), N- {3 - [(4,5-dihydro-3-methyl-5- oxo'-1-phenyl-1H- pyrazol-4-yl) azo] phenyl} -N, N, N-trimethylammonium chloride (Basic Yellow 57), N- [7- hydroxy-8 - [(2-methoxyphenyl) azo] naphth-2-yl] -N, N, N-trimethylammonium chloride (Basic Red 76), N- [4 - [[4- (Dimethylamino) phenyl] [4- (phenylamino) -naphth-1-yl] - methylene] -2, 5-cyclohexadien-1-ylidene] -N-methyl-2-methaniminium chloride (Basic Blue 99), [8 - [(4'-amino-2'-nitrophenyl) azo] -7-hydroxy-naphth-2-yl] - trimethylammonium chloride (Basic Brown 16) and [8 - ((4'-amino-3'-nitrophenyl) azo) - 7-hydroxy-naphth-2-yl] trimethyl ammonium chloride (Basic Brown 17).

Furthermore, the agent according to the invention can also be direct Contain dyes with a thiol group or a dithiol group. Such Dyes have substrate activity for protein disulfide isomerase.

These latter dyes are preferably derived from the above Representatives of the direct dyes.

• - nichtionische Polymere wie beispielsweise VinylpyrrolidonlVinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, VinylpyrrolidonlVinylacrylat- Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/Ntert.Butyl-acrylamid-Terpolymere,
• - Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol,
• - Strukturanten wie Maleinsäure und Milchsäure,
• - haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• - Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - Lösungsmittel und -vermittler wie Ethanol, Isopropanol, n-Butanol, Cyclohexanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• - faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• - quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• - Entschäumer wie Silikone,
• - Farbpigmente zum Anfärben des Mittels,
• - Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol, Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure- Derivate und Triazine,
• - Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• - Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• - Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• - Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmann, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,
• - Cholesterin,
• - Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• - Fettsäurealkanolamide,
• - Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kupplertyp.

Other active ingredients, auxiliaries and additives are, for example

• non-ionic polymers such as, for example, vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• - Anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidonl / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid anhydride copolymers and acrylic acid / ethyl acrylate / acrylamide / ethyl acrylate / acrylate / acrylate / acrylate / acrylamide / ethyl acrylate /
• 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,
• - structurants such as maleic acid and lactic acid,
• hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
• Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, n-butanol, cyclohexanol, 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,
• - color pigments for coloring the agent,
• Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosmann, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - 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,
• - Oxidation dye precursors of the developer and / or coupler type.

Regarding other optional components and the amounts used these components are expressly based on those known to the person skilled in the art relevant manuals, in the case of cosmetic preparations such. B. K. Schrader, basics and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989.

A second object of the invention is the use of an agent which at least one enzyme of the protein disulfide isomerase type (EC 5.3.4.1) and at least one care substance with at least one disulfide - (- S-S-) or Contains thiol group (-SH) and is free of carbohydrate derivatives with at least a disulfide - (- S-S-) or thiol group (-SH) in a care and maintenance process optionally for simultaneous permanent deformation of keratin fibers, especially human hair.

For the preferred embodiments of this agent and for the Definitions of terms apply in the definition of the first subject of Invention said.

A third object of the invention is the use of an agent which contains at least one enzyme of the protein disulfide isomerase type (EC 5.3.4.1) and is free of carbohydrate derivatives with at least one disulfide - (- S-S-) or Thiol group (-SH) in a process for permanent deformation of keratin Fibers, especially human hair.

For the preferred embodiments of this agent and for the Definitions of terms apply in the definition of the first subject of Invention said.

• a) auf die gegebenenfalls angefeuchteten Fasern das zuvor beschriebene erfindungsgemäße enzymhaltige Mittel aufgetragen,
• b) das Mittel für eine Einwirkzeit auf den Fasern belassen
• c) und die Fasern einer Nachbehandlung unterworfen werden.

A fourth object of the invention is a process for the treatment of keratin fibers, in particular human hair, in which

• a) the previously described enzyme-containing agent according to the invention is applied to the optionally moistened fibers,
• b) leave the agent on the fibers for a contact time
• c) and the fibers are subjected to an aftertreatment.

For the composition of the enzyme-containing agent according to the invention and In the relevant embodiments, this applies in the definition of the first Object of the invention said.

The fiber can be moistened using various methods. That's the way it is According to the invention, the hair before step i) of the method Cleaning step, e.g. B. shampooing, subjecting and hair in Toweling after cleaning with a towel. That way get a damp hair. Furthermore, the moistening can be done in the frame a pretreatment by an agent M. The medium M can be on the hair remain or be rinsed off after a contact time. The exposure time of the M is preferably 5 to 45 minutes.

The agent M, if used for the pretreatment, can be used in another Embodiment of the method a reducing agent as a keratin-reducing Contain substance. Examples of suitable reducing agents are Thioglycolic acid, thiolactic acid, thio malic acid, dithiothreitol, mercaptoethanesulfonic acid as well as their salts and esters, cysteamine, cysteine, colored salts and salts of sulphurous acid. The alkali metal or ammonium salts are preferably suitable Thioglycolic acid and / or thiolactic acid and the free acids.

In a further embodiment, agent M contains at least one care substance which contains a thiol group or a disulfide group. Such care substances have a substrate activity for the protein disulfide isomerase. It may be preferred to use the care substance in an amount of 0.001 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.1 to 2% by weight, based on the total agent. use. Care substances which are selected from compounds of the formula I are preferably used,

R ¹ -Y ¹ -G ¹ -XG ² -Y ² -R ² (I)

wherein R ¹ , R ² , Y ¹ , Y ² , G ¹ , G ² and X are as defined above.

In a further embodiment, the agent M contains a direct agent Dye that can be defined as described above.

Agent M preferably has a pH of 4 to 9, particularly preferably from 6 to 8, very particularly preferably from 7.3 to 7.7. It is further preferred that the agent M has the same or similar pH as that after Pretreatment or wetting applied enzyme-containing enzyme according to the invention Medium.

The post-treatment of the fibers can be carried out in different ways. It is According to one embodiment of the invention, the fibers are only one To undergo rinsing, which can be done with water.

According to a further embodiment, the agent M as Post-treatment agent in the process according to the invention for Application come. The agent M is optionally after a optional intermediate rinsing step applied to the fiber. After a dwell time of preferably 5-45 minutes on the fibers, the agent M is rinsed off and the fibers dried.

It is therefore possible in one embodiment of the method, the care substance with a thiol group or disulfide group and the enzyme in succession apply in any order to the keratin-containing fiber. In this The enzyme-containing agent according to the invention cannot have any embodiment Containing care substance, but probably the agent M, which is used as a preliminary or Post-treatment of the fiber is used.

Although these two-step processes can lead to the desired effects it may be preferred to use the process according to the invention in a 1-step process because such a process is easier to use. The Care substance with substrate activity, preferably immediately before use an enzyme-containing composition, and then the Mixture as agent according to the invention in a single step onto the fiber applied.

The process according to the invention can also be carried out as part of an oxidative process Hair coloring process carried out before or after oxidative hair coloring become. Treatment of agents containing keratin with protein disulfide isomerase can the dyeing properties of an oxidative hair dye favorable influence and promote the well-groomed appearance of the hair.

In order to achieve a defined hair deformation, another can Embodiment before step i) of the method according to the invention the hair for mechanical deformation wound on winding aids (winders, papillots) become. Experience has shown that the hair can be placed particularly well on the changing aids wrap when it's damp. Consequently, the hair should be moistened before or during the introduction of the winding aids. In this embodiment the fiber can also be moistened with the agent according to the invention.

The enzyme-containing agent according to the invention is after an exposure time of 3 to Rinsed out for 120 minutes. This rinsing can be done with pure water. In most cases, exposure times of 15 to 30 minutes have turned out to be proven sufficiently.

Regardless of the course of the method according to the invention, it has proven to be proven advantageous, the enzyme at a temperature of 18 to 55 ° C, especially from 25 to 50 ° C to use.

Claims (35)

1. Agent for the cosmetic treatment of keratin fibers, in particular human hair, characterized in that the agent contains at least one enzyme of the protein disulfide isomerase type (EC 5.3.4.1) and is free of carbohydrate derivatives with at least one disulfide (-SS-) or thiol group (-SH). 2. Composition according to claim 1, characterized in that it is the enzyme in a Contains from 0.1 to 2000 units of enzyme. 3. Agent according to one of claims 1 to 2, characterized in that the Has a pH of 4 to 9. 4. Agent according to claim 3, characterized in that the agent has a pH Value from 7.3 to 7.7 has: 5. Agent according to one of claims 1 to 4, characterized in that the Average 0.0001 to 0.5% by weight of a keratin reducing agent contains. 6. Agent according to one of claims 1 to 5, characterized in that the Contains at least one complexing agent. 7. Agent according to one of claims 1 to 6, characterized in that the Contains at least one surfactant. 8. Agent according to one of claims 1 to 7, characterized in that the Contains at least one thickener. 9. Agent according to one of claims 1 to 8, characterized in that it additionally contains at least one substantive dye. 10. Agent according to one of claims 1 to 9, characterized in that the Agent additionally contains at least one dye that has a thiol group (-SH) or a disulfide group (-S-S-) in the molecule. 11. Agent according to one of claims 1 to 10, characterized in that the Agent additionally contains at least one care substance that contains a thiol group (-SH) or a disulfide group (-S-S-) in the molecule. 12. Composition according to claim 11, characterized in that the care substance in an amount of 0.001-10 wt .-% based on the total agent is included. 13. Composition according to one of claims 11 or 12, characterized in that the care substance is selected from compounds according to formula I,
R ¹ -Y ¹ -G ¹ -XG ² -Y ² -R ² (I)
wherein,
X represents a thio group (-S-) or a disulfide group (-SS-)
G ₁ , G ₂ independently of one another represent a direct bond, a C ₁ -C ₁₀ alkylene group, an arylene group or an arylene C ₁ -C ₁₀ alkylene group
where G ^{2 is} a direct bond when X is a thio group.
Y ¹ , Y ² independently of one another represent a direct bond, an azo group, a group -NH-C (O) -, a group -OC (O) -, a thio group (-S-) or an oxy group (-O- )
and Y ² means a direct bond when X represents a thio group,
R ¹ , R ² independently of one another represent a hair care component, where R ¹ and R ^{2 may be the} same or different and the radical R ^{2 represents} a hydrogen atom if X denotes a thio group. 14. Composition according to claim 13, characterized in that X is a disulfide group is. 15. Agent according to one of claims 13 or 14, characterized in that the care substance is derived from linear and / or branched and saturated and / or unsaturated fatty acids, linear and / or branched and saturated and / or unsaturated alcohols, Alkylamidoamines, amino acids and their derivatives, peptides, Polyhydroxy compounds, silicones, quaternized ammonium compounds, Vitamins, pantolactone and hydroxy acids. 16. Composition according to claim 15, characterized in that the linear and / or branched and saturated and / or unsaturated fatty acids are selected from formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, Toluoylsäure, hydratropic , Atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid, 4,4'-dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7 - Napthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane icarboxylic acid and the dicarboxylic acids selected from the group formed by compounds of the general formula (II),


in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH group and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (II) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (II) by addition of a molecule of water to the double bond in the cyclohexene ring. 17. Composition according to claim 15, characterized in that the linear and / or branched and saturated and / or unsaturated alcohols selected are made of ethanol, butanol, hexanol, lauryl alcohol, myristyl alcohol, Cetyl alcohol, stearyl alcohol, oleyl alcohol and linoleyl alcohol. 18. Composition according to claim 15, characterized in that the amino acids and whose derivatives are selected from alanine, arginine, cysteine, glutamine, Glycine, histidine, lysine, leucine, ornithine, isoleucine, serine, tyrosine, tryptophan, Valine and phenylalanine and their physiologically tolerable salts, Amino acid amides, especially the di-, tri- or tetra-peptides, and Amino acid esters and phosphorylated amino acids. 19. Composition according to claim 15, characterized in that the peptides are selected from oligopeptides, in particular elastin, collagen, Keratin, milk protein, soy protein and wheat protein hydrolyzates. 20. Composition according to claim 15, characterized in that the Polyhydroxy compounds are selected from glucamine, glycerol, mono- or diglycerides, 2-ethyl-1,3-hexanediol, 2-hydroxymethylpropane triol, Glycols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, 1,3-butanediol, citric acid, malic acid, tartaric acid, Pentahydroxyhexanoic acid, tetrahydroxypentanoic acid and the derivatives and / or optionally the physiologically tolerable salts of aforementioned connections. 21. Composition according to claim 15, characterized in that the silicones are selected from cyclomethicones, octamethylcyclotetrasiloxane, Decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Hexamethyldisiloxane, dimethicone copolymers, polysiloxanes and quaternized polysiloxanes. 22. Composition according to claim 15, characterized in that the quaternized Ammonium compounds are selected from esterquats and / or their Derivatives, alkylammonium halides, especially chlorides and bromides, especially cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. 23. A composition according to claim 15, characterized in that the hydroxy acids are selected from α-hydroxy fatty acids, β-hydroxy fatty acids, α- Keto fatty acids, β-keto fatty acids and / or their physiologically compatible Salt. 24. Use of the agent according to one of claims 11 to 23 in one Process for. Maintain and, if necessary, permanent at the same time Deformation of keratin fibers, especially human hair. 25. Use of the agent according to one of claims 1 to 11 for permanent Deformation of keratin fibers, especially human hair. 26. A process for the treatment of keratin fibers, in particular human hair, characterized in that a) an agent according to one of claims 1 to 23 is applied to the optionally moistened fibers, b) leave the agent on the fibers for an exposure time c) and the fibers are subjected to an aftertreatment. 27. The method according to claim 26, characterized in that before the step i) the fiber is wound onto a winding aid for mechanical deformation becomes. 28. The method according to claim 27, characterized in that the fiber before or is moistened during winding. 29. The method according to any one of claims 26 to 28, characterized in that that the fiber is moistened with an aqueous agent M. 30. The method according to any one of claims 26 to 28, characterized in that the fiber is treated with an agent M. 31. The method according to any one of claims 29 or 30, characterized in that that the agent M contains at least one substantive dye. 32. The method according to any one of claims 29 to 31, characterized in that that the agent M at least one care substance with a thiol group or contains a disulfide group. 33. The method according to any one of claims 29 to 32, characterized in that that the agent M has a pH between 4 and 9. 34. The method according to claim 28, characterized in that the fiber with an agent according to one of claims 1 to 24 is pre-moistened. 35. The method according to any one of claims 26 to 34, characterized in that; that the exposure time in step ii) is 3 to 120 minutes.