WO2006021350A1

WO2006021350A1 - Novel agent for treating keratin fibres

Info

Publication number: WO2006021350A1
Application number: PCT/EP2005/008875
Authority: WO
Inventors: Gabriele Weser; Marlene Henke
Original assignee: Hans Schwarzkopf & Henkel Gmbh & Co. Kg
Priority date: 2004-08-26
Filing date: 2005-08-16
Publication date: 2006-03-02
Also published as: DE102004041573A1

Abstract

The invention relates to an agent for treating keratin fibres, said agent containing at least one protease and at least one other constituent selected from protein hydrolysates, vitamins, provitamins and vitamin precursors, in addition to the derivatives thereof. The invention also relates to corresponding uses and methods for the treatment of keratin fibres.

Description

New agent for the treatment of keratinic fibers

The present invention relates to an agent for the treatment of keratinic fibers, which contains at least one protease and at least one further component which is selected from protein hydrolysates as well as vitamins, provitamins and vitamin precursors and derivatives thereof. Furthermore, the invention relates to corresponding uses and methods for the treatment of keratinic fibers.

Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures, and the bleaching, dyeing and shaping of the hair with colorants, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role. As a result of this behavior, hair is exposed in many ways to straining influences that have a negative effect on the surface structure.

Research has shown that 70 percent of women wash their hair several times a week, 8 percent a day. This care behavior means that the so-called "all-purpose shampoos" are replaced by a variety of needs-based and gentler formulations. At the same time, the need for supplementary care products is also growing, as mechanical stresses such as combing, blow-drying or rubbing on clothing strain the hair. In addition, chemical treatments such. B. perms or color changes in addition to stress. A hair is washed, blown and brushed on average 400 times until it reaches a length of 20 cm. Under the microscope, undamaged hair is comparable to a pine cone. It is surrounded by a closed scale layer. When attacked hair this layer is no longer closed. The scales are standing and break out partially. The incident light is no longer reflected, the hair looks dull and dull. Although hair treatments alleviate worse problems, they often make the hair "heavy" and, in many cases, only act on the surface of the hair so that they can not completely regenerate it.

There has therefore been no lack of efforts to counteract or prevent the damage to the hair structure by using care ingredients. Various care components have been developed which are used specifically as aftertreatment agent for damaged hair. Further, the hair treatment agents per se, such as the fixer in the context of a permanent wave treatment or the colorants, added with additional care agents. For example, it has been proposed in DE-A1-196 17 569 to use special amino acids as care substances.

DE-C-197 09 334 discloses the use of proteolytically active enzymes for the enzymatic dissolution or detachment of the spread cuticular edges of the hair causing an undesired roughness of the hair surface.

It has now surprisingly been found that the combined use of proteolytically active enzymes and protein hydrolysates and / or vitamins, vitamins and vitamin precursors as well as their derivatives in keratinic fibers, in particular hair, causes a considerable repair effect. As a result, the condition of the hair during the hair treatment is improved from the inside by the fact that the care substances used penetrate into the hair to be treated. This leads to a regeneration or structure stabilization of the hair, which is not limited exclusively to the hair surface.

The present invention therefore provides an agent for treating kera¬ tinischer fibers containing at least one protease and at least one further component which is selected from protein hydrolysates and vitamins, provitamins and vitamin precursors and their derivatives. The above-explained combination treatment of the keratinic fibers with the agent according to the invention advantageously leads to an improvement in the damaged structure of the fibers.

The agent according to the invention for the treatment of keratinic fibers may contain one protease or else several mutually different proteases.

Proteases cleave peptide bonds within an amino acid chain. This can improve desquamation, increase pore size, and expose amino acid side chains. Thus, the penetration of the repair agents into the hair can be improved.

According to the invention, pro- and / or eukaryotic proteases can be used. Among other things, they differ in their gap specificity (specifically for specific amino acids in a chain or at random). For example, trypsin cleaves peptide bonds after the amino acids arginine and lysine. In this case, free amino groups are formed on the protein side chains, with which corresponding reactions are possible. The keratin structure is less strongly attacked than with the use of nonspecifically cleaving proteases such. bak¬ terieller subtilisins.

In principle, all proteases can be used in the agent according to the invention, in particular the enzymes classified under EC 3.4 - Acting on peptide bonds (peptidases) which are available for example on the Internet under the URL http://www.chem.qmul.ac.Uk/iubmb / enzymes / EC3 / 4 / are listed.

Preferred proteases according to the invention are the serine endopeptidases (EC3.4.21) and the cysteine endopeptidases (EC3.4.22). Particularly preferred proteases according to the invention are selected from subtilisin {EC 3.4.21.62), papain {EC 3.4.22.2) and bromelain (EC 3.4.22.32).

The enzymes are preferably present in the agent according to the invention in amounts of from 0.005 to 10% by weight, based on the total preparation. Amounts of 0.01 to 5 wt .-% are particularly preferred.

The at least one further component is preferably present in the agent according to the invention in amounts of from 0.005 to 10% by weight, based on the total preparation. Amounts of 0.01 to 2 wt .-% are particularly preferred.

The agent according to the invention may comprise protein hydrolyzates, preferably cationized protein hydrolysates, wherein the protein hydrolyzate on which the animal is based, for example from collagen, milk or keratin, from the plant, for example from wheat, maize, rice, potatoes, soya or almonds, from marine life forms , for example from fish collagen or algae, or biotechnologically obtained protein hydrolysates. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of from 100 to 25,000 daltons, preferably from 250 to 5,000 daltons. Furthermore, cationic protein hydrolyzates are understood to mean quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or of the amino acids is frequently carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) -ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, letry TOI, and Fragrance Association 1101 17 ^th Street, NW, Suite 300, Washington, DC 20036-4702) Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimium Hydroxypropyl Hydrolyzed Silica, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl SiCl Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydr olyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropylpltrimonium Hydrolyzed Silicon, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Lauridonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurodimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimony Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimony Hydroxypropyl Hydrolyzed Silicon, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Ste Ardimony Hydroxypropyl Hydrolyzed Sickle, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternary nium-79 Hydrolyzed Sick, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein. Very particular preference is given to the protein hydrolyzates based on wheat which are available under the trade names Gluadin WQ and Gluadin WLM.

It has proved to be preferred according to the invention if the agent contains at least one cationic protein hydrolyzate. In this case, the effect according to the invention can be increased still further if the agents of the present invention contain at least one cationic and at least one nonionic protein hydrolyzate.

Furthermore, it has proved to be preferred according to the invention if the agents contain at least one wheat protein hydrolyzate.

Furthermore, the agent according to the invention may contain vitamins, provitamins and vitamin precursor and their derivatives.

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

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

The vitamin B group or the vitamin B complex include - Vitamin Bi (thiamine) - Vitamin B2 (riboflavin)

- Vitamin B3. The compounds nicotinic acid and nicotinic acid amide (niacinamide) are frequently used under this name. Preferred according to the invention is the nicotinic acid amide, which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent.

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

- Vitamin Bβ (pyridoxine and pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the compositions according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total agent. The use in the form of the palmitic acid ester, the glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.

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

Vitamin F. The term "vitamin F" is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid. Vitamin H. The vitamin H is the compound (3aS, 4S, 6afi) -2-oxohexahydrothienol [3,4-c /] imidazole-4-valeric acid, for which, however, the trivial name biotin has meanwhile prevailed , Biotin is contained in the agents used according to the invention preferably in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight.

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

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinic acid amide and biotin are particularly preferred. Panthenol, pantolactone and nicotinic acid amide are very particularly preferred. Pantolactone has proven particularly suitable according to the invention.

Within the scope of a particularly preferred embodiment of the present invention, the agent according to the invention contains at least one protein hydrolyzate and at least one vitamin, provitamin or a vitamin precursor and one of its derivatives.

Very particularly preferred for the purposes of the present invention is an active ingredient combination of pantolactone, at least one cationic and at least one nonionic wheat protein hydrolyzate. This is beispiels¬ be achieved through the use of pantolactone in combination with the Handelsproduk¬ th Gluadin® ^® WQ and Gluadin® ^® WLM.

With regard to the time schedule, the use of the agent according to the invention is subject to no restrictions. It is in principle possible to apply two separate preparations comprising (a) the protease and (b) the at least one further component in succession in any order on the fibers. Here, however, between the steps (a) and (b) should not be too big time interval, so that the fibers do not dry between the steps.

Although the composition according to the invention can in principle remain on the hair, the agent is preferably rinsed out after an exposure time of 1 minute to 60 hours. This rinsing can be carried out with pure water or a conventional shampoo. Exposure times of 5 to 15 minutes have proven sufficient in most cases.

Regardless of the exact sequence of the pretreatment, it has proved to be vorteil¬ way, composition of the invention at a temperature of 20 to 55 ⁰ C, in particular of 35 to 40 ⁰ C to apply.

With regard to the way in which the composition according to the invention is applied to the keratinic fiber, in particular human hair, there are no fundamental restrictions. For example, creams, solutions, solutions, waters, emulsions such as W / O, O / W, PIT emulsions (emulsions according to the teaching of phase inversion, PIT) are mentioned as the preparation of these preparations containing the agent according to the invention ), Microemulsions and multiple emulsions, gels, sprays, aerosols and foam aerosols. These are usually formu lated on an aqueous or aqueous-alcoholic basis. The alcoholic component used are lower alkanols and polyols such as propylene glycol and glycerol. Ethanol and isopropanol are preferred alcohols. Water and alcohol may be present in the aqueous alcoholic base in a weight ratio of 1:10 to 10: 1. Water and aqueous-alcoholic mixtures which contain up to 50% by weight, in particular up to 25% by weight, of alcohol, based on the mixture of alcohol / water, may be preferred bases according to the invention. The pH of these preparations may in principle be between 2 and 11. It is preferably between 2 and 7, with values of 3 to 5 being particularly preferred. To adjust this pH, virtually any acid or base that can be used for cosmetic purposes can be used. Usually acids are used as acids. applies. By-acids are understood to mean those acids which are absorbed as part of the usual food intake and have positive effects on the human organism. Eat acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. In the context of the invention, the use of citric acid and lactic acid is particularly preferred. Preferred bases are ammonia, alkali hydroxides, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

The agent can be confectioned as a single-chamber system or as a two-chamber system. In a two-chamber system, typically the enzyme component (protease) and the repair substance component (protein hydrolysates, pantolactone, panthenol or niacinamide) are spatially separated from one another.

A further subject of the present invention is a two-part kit for the treatment of keratinic fibers which is characterized in that it comprises a) the enzyme component (protease) and b) the repair substance component (protein hydrolysates, pantolactone, panthenol or niacinamide).

In addition to the enzyme which is absolutely necessary according to the invention and the at least one further component mentioned above, the agent may in principle contain all other components known to the person skilled in the art for such cosmetic compositions.

Other active ingredients, auxiliaries and additives are, for example

anionic surfactants, in particular alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, soaps and sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid. remono-alkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

ampholytic surfactants such as, for example, N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group,

nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,

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

- structurants such as maleic acid and lactic acid,

hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and also silicone oils,

Perfume oils, dimethylisosorbide and cyclodextrins,

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

- symmetrical and unsymmetrical, linear and branched dialkyl ethers having a total of from 12 to 36 carbon 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 and di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl n-undecyl ether, and di tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether, Fatty alcohols, especially linear and / or saturated fatty alcohols with 8 to 30

C atoms, and monoesters of fatty acids with alcohols having 6 to 24 carbon atoms,

fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides, such as, for example, glucose, galactose, fructose, fructose and lactose,

- Conditioning agents such as paraffin oils, vegetable oils, eg. Sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil and phospholipids, for example soya lecithin, egg lecithin and cephalins,

quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate,

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

- light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

- Other substances for adjusting the pH, such as α- and ß-hydroxycarboxylic acids

- active substances such as allantoin and bisabolol,

- cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

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

Fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

- swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

- pigments,

- Reducing agents such. Thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thiomalic acid and α-mercaptoethanesulfonic acid, Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

- antioxidants.

The composition of the invention may also contain surfactants. These may be anionic, ampholytic, zwitterionic or nonionic surfactants as well as cationic surfactants. The person skilled in the art can optionally check a possible influence of the various surfactants on the activity of the protease by simple preliminary tests.

In a preferred embodiment of the present invention, a combination of anionic and nonionic surfactants or a combination of anionic and amphoteric surfactants is used.

However, it has proven advantageous in individual cases to select the surfactants from ampho¬ teren or nonionic surfactants.

Suitable anionic surfactants in the compositions according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups can be contained in the molecule.

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

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group, C ₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

C ₈ -C ₂₂ -Alkylmono- and oligoglycosides and their ethoxylated analogs and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These compounds are characterized by the following parameters.

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

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹ consists essentially of Cs and C-io-alkyl groups, consisting essentially of C ₁₂ - and C ^ alkyl groups, consisting essentially of C ₈ - to C-iβ-alkyl groups or substantially C ₁₂ - to Ci ₆ alkyl groups. As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, alto-rose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks 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 from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further ingredient of the preparations according to the invention in the event that an effect of the perfume oil on the hair that extends beyond the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs can contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO.sub.1 or -SOa.sub.2 group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglyci- nate, for example the Kokosacylaminopropyl-dimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 C-men in the alkyl or acyl group and Kokosacylaminoethylhydroxyethyl- carboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are surface active compounds which, apart from a C ₈ -C ₈ alkyl or acyl group in the molecule min¬ least one free amino group and at least one -COOH or -SO ₃ H group and capable of forming inner salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkyl-amidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ - ₁₈ - sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such ester-quats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this substance group Sub¬ presents under the name Tegoamid ^® S 18 commercially erhältli¬ che stearamidopropyl dimethylamine is.

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

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

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

Another object of the present invention is the use of at least one protease and at least one further component which is selected from protein hydrolysates and vitamins, provitamins and vitamin precursors and derivatives thereof for improving the structure keratini¬ shear fibers.

A further subject of the present invention is a process for improving the structure of keratinic fibers, characterized in that an agent according to the invention is applied to the keratinic fibers.

The following examples illustrate the invention without, however, restricting it to:

Example 1:

hair conditioner

Eumulgin ^® B2 0.3

Cetyl / stearyl alcohol 3,3

Isopropyl myristate 0.5

Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart® ^® A-CA 2.0

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5

Subtilisin or papain 0.5

Phenonip ^® 0.8

Water ad 100 pH = 7.0

Example 2:

hair conditioner

Eumulgin ^® B2 0.3

Cetyl / stearyl alcohol 3,3

Isopropyl myristate 0.5

Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart ^® L 80 2.0

Gluadin WQ ^® 0.5

Gluadin ^® WLM 0.2

Pantolactone 1, 0

Subtilisin or papain 1, 0

Citric acid 0.4 Phenonip ^® 0.8

Water ad 100 pH 7.0

Example 3:

Hair Conditioner (rinse off)

Dehyquart ^® F75 4.0

Cetyl / stearyl alcohol 4.0

Paraffin oil perliquidum 15 cSt. DAB 9 1, 5

Dehyquart® ^® A-CA 4.0

Salcare ^® SC 96 0.5

Gluadin® ^® WQ 1, 0

Gluadin® ^® WLM 1, 0

Pantolactone 0.5

Subtilisin or papain 0.2

Citric acid 0.15

Phenonip ^® 0.8

Water ad 100 pH = 7.0

Example 4:

Hair Conditioner (rinse off)

Dehyquart ^® L80 4.0

Cetyl / stearyl alcohol 6.0

Paraffin oil perliquidum 15 cSt. DAB 9 2.0

Rewoquat ^® W 75 2.0

Sepigel ^® 305 0.5

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5 Subtilisin or papain 0.5

Citric acid 0.15

Phenonip ^® 0.8

Water ad 100 pH = 7.0

Example 5:

Hair cure (remaining on the hair)

Dehyquart ^® F75 0.3

Salcare ^® SC 96 5.0

Dow ^Corning® 200 Fluid, 5 cSt. 1, 5

Gafquat ^® 755N 1, 5

Biodocarb ^® 0.8

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5

Subtilisin or papain 0.5

Perfume oil 0.25

Water ad 100 pH = 7.0

Example 6:

Hair cure (remaining on the hair)

Sepigel ^® 305 5.0

Dow Coming ^® Q2-5220 5 cSt. 1, 5

Genamin DSAC ^® 0.3

Phenonip ^® 0.8

Gluadin WQ ^® 0.5

Gluadin® ^® WLM 0.8

Pantolactone 1, 0 Subtilisin or papain 0.8

Perfume oil 0.25

Water ad 100 pH = 7.0

Example 7:

Shampoo (in%):

Laureth sulfate 25% 40

Citric acid 0.1

Sodium benzoate 0.5

Disodium Cocoamphodiacetate 6.0

Salicylic acid 0.1

Hydrotriticum ^® WQ 1, 0

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5

Subtilisin or papain 0.2

Cetiol ^® HE 0.5

Perfume 0.4

NaCl 0.5 water Ad 100

Example 8:

Shampoo (in%):

Laureth sulfate 25% (alkaline dilution) 25.0

Citric Acid Mono Regular 0.3

Timiron ^® 0.5

Sodium benzoate 0.5

Panthenol 75 L 0.2 Euperlan PK 3000 ^® 8.0

Plantacare ^® 818 UP 2.0

Uvinui ^® MS40 1 0

Salicylic acid 0.2

Ajidew ^® NI-50 2.0

Cutina ^® HR Ground 0.5

Cetiol ^® HE 1, 0 Citric acid 0.03

^Jaguar® Excel 0.3

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5

Subtilisin or papain 0.5

Sodium chloride 0.3 water Ad 100

Example 9:

Shampoo (in%):

Laureth sulfate 25% (alkaline dilution) 50

Citric acid 0.4

Arlypon F ^® 0.5

Antil ^® 171 0.3

Wheat protein hydrolyzate Cationized 1, 5

Sodium benzoate 0.5

Euperlan ^® PK 3000 6.0

Cocamidopropyl Betaine 45% 5.0

Salicylic acid 0.2

Silsoft ^® A-858 0.3

Gluadin® ^® WQ 1.0

Gluadin® ^® WLM 1, 0

Pantolactone 0.5 Subtilisin or papain 0.2

Cutina ^® HR 0.2

Cetiol ^® HE 1, 0

Water Ad 100

Example 10:

hair styling gel:

Desalinated water ad 100

Synthalen® ^® K 0.6

Neutral ^® TE 0.5

Glycerin 8.00

Ethyl alcohol denatured 96% by volume FIs 30.00

Gluadin WQ ^® 0.5

Gluadin ^® WLM 0.5

Pantolactone 1, 0

Subtilisin or papain 0.2

Polyethylene glycol 2.00

PVP / VA W-635 6,50

Cremophor ^® RH 40 1, 00

Perfume 0.50 pH = 7.0

Example 11:

Hairspray:

Amphomer ^® 3.00

Luviskol ^® VA 37 16.00

Amino-methyl-PropanoMOO 0.60

Isopropyl myristate 0.12

Gluadin WQ ^® 0.5

Gluadin ^® WLM 0.5 Pantolactone 0.2

Subtilisin or papain 1, 0

Perfume 0.20

Desalinated water ad 100

Ethyl alcohol 67.50 pH = 7.0

Example 12:

Hair Tonic:

Desalinated water ad 100

Panthenol 75 0.1

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5

Pantolactone 0.5

Subtilisin or papain 0.5

Carbopol ^® 0.1

Neutral ^® TE 0.10

Ethyl alcohol 30.0 pH = 7.0

Example 13:

Hair conditioner as in example 1, as 2-K system: 1st chamber:

Eumulgin ^® B2 0.3

Cetyl / stearyl alcohol 3,3

Isopropyl myristate 0.5

Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart® ^® A-CA 2.0

Gluadin WQ ^® 0.2

Gluadin ^® WLM 0.5 Pantolactone 0.5

Phenonip ^® 0.8

Water ad 100 pH = 4.0

2nd chamber

Subtilisin or papain 0.5

(or papaya extract 1, 0)

Water ad 100

Example 14:

Conditioner analogous to Ex. 6, but in two application steps: pretreatment with enzyme

Subtilisin or papain 0.5

(or papaya extract 1, 0)

Water ad 100

Aftercare with care / repair product:

Sepigel ^® 305 5.0

Dow Corning ^® Q2-5220 5 cSt. 1, 5

Genamin DSAC ^® 0.3

Phenonip ^® 0.8

Gluadin WQ ^® 0.5

Gluadin® ^® WLM 0.8

Pantolactone 1, 0

Perfume oil 0.25

Water ad 100 Example 15:

Test pattern:

Execution:

Pretreatment of the hair strands:

The hair (Alkinco 6634) were before the zero measurement with a Texapon.RTM ^® NSO - pre-purified solution (10% AS) and then permed standard. That is, 2 g of permanent wave gel (Poly-Lock 1) were distributed over 1 g of hair strand. Subsequently, after 40 minutes of exposure to the gel under standard conditions, it was rinsed with cold tap water for 60 seconds. This was followed by fixing with 2 g of Poly-Lock 2 per 1 g of hair strand over a period of 10 minutes.

Product application:

A strand of hair was treated with an aqueous solution of the respective active ingredient mixture. The immersion time was 15 minutes at room temperature. The hair was then rinsed out for 30 seconds under cold, flowing water and air-dried. DSC measurements:

To verify the repair effect, DSC measurements were performed. The tresses were cut into small pieces (~ 1 mm) and then transferred to 5 aliquots of each strand of hair in the DSC measuring vessels. After adding aqua deion. The measurements were carried out in a temperature range of 110-170 ⁰ C, at 10 ° C / min. The melting point (peak maximum in [ ⁰ C]) and the enthalpy of denaturation (area under the peak in [J / g]) were determined.

The following measured values (significance level> 99%) have resulted:

1st series of measurements (leave-on)

Zero measurement 152.6 ° C

Gluadin ^® WLM, pantolactone, Exfocellia 153.8 ° C

2nd series of measurements (rinse-off)

Zero measurement 151, 9 ⁰ C

Gluadin® ^® WLM and Exfocellia 153.7 ⁰ C

Gluadin ^® WLM, pantolactone, Exfocellia 154.2 ° C

Exfocellia (comparative experiment) 152.7 ° C (no significant improvement)

3rd measurement series (leave-on)

Zero measurement 151, 9 ⁰ C

Gluadin® ^® WQ, Gluadin® ^® WLM, papaya fruit HPG 153.0 ⁰ C

Gluadin ^® WLM, Papaya Fruit HPG 153.3 ° C

Gluadin® ^® WLM, pantolactone, papaya fruit HPG 153.9 ° C 4th measurement series (leave-on)

Zero measurement 152.9 ° C

Gluadin® ^® WQ (Comparison) 153.3 ° C (no significant improvement)

Gluadin® ^® WLM (Comparison) 153.7 ° C (no significant improvement)

δ.Measurements (Rinse-off)

Zero measurement 152.9 ⁰ C

Gluadin® ^® WLM, papaya fruit HPG, pantolactone 154.4 ° C

6th series of measurements (rinse-off)

Zero measurement 153.9 ⁰ C

Gluadin® ^® WQ (Comparison) 153.6 ° C (no significant improvement)

Gluadin® ^® WLM (Comparison) 154.6 ° C (no significant improvement)

List of used commercial products

The commercial products used in the examples are defined as follows:

Ajidew ^® NL50 sodium salt of pyrrolidone (substance content about 48-52% Aktiv¬; INCI name: Sodium PCA) (Ajino- moto)

Amphomer ^® INCI name: Otylacrylamide / Acrylates / Butyl aminoethyl Methacrylate Copolymer (National Starci) Antil ^® 171 polyol fatty acid esters (INCI name: PEG-18 glyceryl ryl Oleate / Cocoate) (Goldschmidt) Arlypon F ^® C12 14 fatty alcohol with about 2.5 EO-units (INCI name: Laureth-2) (Cognis) Biodocarb ^® 3-iodo-2-n-proinyl butylcarbamate (INCI name: lo- dopropynyl Butylcarbamate) (Milker & Grüning)

Carbopol ^® Polyarcylsäure (INCI name: Carbomer) (Noveon) Cetiol ^® HE Kokosmonglycerid with about 7.3 EO units (INCI name: PEG-7 glyceryl cocoate) (Cognis) Cremophor ^® RH40 hydrogenated castor oil with 40-45 EO units (INCI name: PEG-40 Hydrogenated Castor Oil) (BASF) Cutina ^® HR hydrogenated castor oil (INCI name: Hydrogenated Castor Oil) (Cognis) Dehyquart® ^® A- CA trimethylhexadecylammonium chloride (about 24-26% active substance; INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis)

Dehyquart ^® F75 fatty alcohols Methyltriethanolammoniummethylsulfat--dialkyl-mixture (INCI name: Distearoylethyl Hydroxyethylmonium Methosulfate, Cetearyl Alcohol) (HENKEL) Dehyquart ^® L80 bis (Cocoylethyl) -hydroxyethyl-methyl-ammonium methosulfate (approximately 76% active ingredient in propylene glycol; INCI Designation: dicocoylethyl hydroxyethylmonium methosulfate, propylene glycol) (Henkel)

Dow Corning ^® 200 fluid polydimethylsiloxane (INCI designation: Dimethicone) (Dow Corning) Dow Corning ^® Q2-5220 silicone glycol copolymer (INCI name: dimethicone copolyol) (Dow Corning) Eumulgin B2 ^® cetylstearyl alcohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis) Euperlan ^® PK3000 about 60-64% solids; INCI name: Glycol Distearate, Glycerol, Laureth-4, Cocamidopropyl Betaine) (Cognis)

Gafquat ^® 755 dimethylaminoethyl methacrylate-vinylpyrrolidone copolymer, quaternized with diethyl sulfate (ca. 19% solids in water; INCI name: Polyquaternium-11) (ISP)

Genamin ^® DSAC Dimethyldistearylammonium chloride (INCI name: Distearyldimonium Chloride) (Clariant)

Gluadin ^® WLM wheat protein hydrolyzate (about 21-24% solids, INCI name: Hydrolyzed Wheat Protein) (Cognis)

Gluadin ^® WQ wheat protein hydrolyzate (about 31-35% solids, INCI name: Aqua (Water), Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein, Ethylparaben, Methylparaben) (Cognis)

Hydrotriticum ^® WQ approx. 26-30% solids; INCI name: Aqua (Water), Hydroxypropyltrimonium Hydrolyzed Wheat Protein; (Croda) Jaguar Excel ^® Guarhydroxypropyltrimethylammoniumchlorid (about 89% active substance content; INCI name: Guar Hydroxypro¬ pyltrimonium Chloride) (Rhodia) Neutral ^® TE N, N, N ', N', - tetrakis (2-hydroxypropyl) ethylenediamine (INCI name: tetrahydroxypropyl ethylene diamine) (BASF) Phenonip ¹⁰ hydroxybenzoic acid methyl ester hydroxybenzoic acid ethylester hydroxybenzoic acid propyl ester hydroxybenzoic acid butyl ester phenoxyethanol mixture (about 28% active ingredient, INCI name: phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben) (NIPA)

Plantacare ^® 818UP C8-14 alkyl polyglucoside (ca. 51-53% Akticsubstanzgehalt; INCI name: Coco-Glucoside, Aqua (Water)) (Cog nis) PVP / VA W-635 vinyl pyrrolidone vinyl acetate copolymer (Ca.48-52 % Fest¬ body in water; INCI name: VP / VA copolymer) (ISP) Rewoquat W75 ^® l-methyl-2-nortalgalkyl-3-talgfettsäureamidoethyl- imidazolinium methosulphate (75% active substance in production pylenglykol; INCI Name: Quaternium-27, Propylene Glycol) (WITCO)

Salcare ^® SC 96 about 50% active ingredient content; INCI name: Polyquaternium-37, Propylene Glycol Dicaprylate / Dicaprate, PPG-1 Trideceth-6 (CIBA)

Sepigel ^® 305 about 45-49% solids; INCI name: polyacrylamides amides, C13-14 isoparaffin, laureth-7) (Seppic) Silsoft ^® A 858 INCI name: DEA PG-propyl PEG / PPG-18/21 dimethyl thicone) (GE Silicones) Synthalen ^® K polyacrylic acid (ca. 89% active substance content; INCI name: Carbomer) (3V Sigma) Uvinul ^® MS40 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (100% active substance content; INCI name: Benzophenone- 4) (BASF)

Claims

claims

1. A composition for the treatment of keratinic fibers, containing at least one protease and at least one further component which is selected from protein tolysates and vitamins, provitamins and vitamin precursors and derivatives thereof.

2. Composition according to claim 1, characterized in that the protease is selected from among serine endopeptidases and cysteine endopeptidases, in particular under subtilisin, papain and bromelain.

3. Composition according to claim 1 or 2, characterized in that the enzymes in amounts of 0.005 to 10 wt .-%, based on the total preparation, are contained, in particular in. Amounts of 0.01 to 5 wt .-%.

4. Composition according to one of the preceding claims, characterized in that the at least one further component in amounts of 0.005 to 10 wt .-%, based on the total preparation, is contained, preferably in. Amounts of 0.01 to 2 wt. -%.

5. Composition according to one of the preceding claims, characterized in that it contains at least one protein hydrolyzate and at least one vitamin, vitamin Pro or a vitamin precursor and one of their derivatives.

6. Composition according to one of the preceding claims, characterized in that it contains as vitamin, provitamin or a vitamin precursor and one of their derivatives pantolactone.

7. Composition according to one of the preceding claims, characterized in that it contains at least one cationic protein hydrolyzate.

8. Composition according to one of the preceding claims, characterized in that it contains at least one wheat protein hydrolyzate.

9. Composition according to one of the preceding claims, characterized in that it contains at least one cationic and at least one nonionic protein hydrolyzate.

10. Composition according to one of the preceding claims, characterized in that it contains pantolactone, a cationic and a nonionic Weizenpro¬ teinhydrolysat.

11.Mittel according to any one of the preceding claims, characterized in that it is made up as Einkammersystem or as a two-chamber system, wherein in a two-chamber system, the enzyme component and the Repairstαffkomponente are spatially separated.

12. Use of at least one protease and at least one further component which is selected from protein hydrolysates as well as vitamins, provitamins and vitamin precursors and derivatives thereof for improving the structure of keratinic fibers.

13. A process for improving the structure of keratinic fibers, characterized ge indicates that applying an inventive agent to the keratinic fibers.

14. A two-part kit for the treatment of keratinic fibers, characterized gekennzeich¬ net, that a) a first region containing the protease and b) a second region containing the one further component aus¬ selected from protein hydrolysates and vitamins, provitamins and Vitamin precursors and their derivatives.