WO2001021139A2 - Method for restructuring keratin fibers using an enzyme of the transglutaminase type - Google Patents

Abstract

The invention relates to a method for restructuring keratin fibers. According to the inventive method, (A) at least one enzyme of the transglutaminase type and (B) at least one active substance that has a substrate activity for said enzyme are applied on the fibers. The inventive method allows the restructurization of damaged fibers.

Description

 "Process for Restructuring Keratinic Fibers'

The invention relates to a method for restructuring keratin fibers.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or shading the color of the head hair play an outstanding role. This behavior means that hair is exposed to stressful influences in many ways, which have a negative effect on the surface structure.

There has been no lack of efforts to counteract the damage to the hair structure and to develop restructuring techniques. A wide range of care components have been developed that are used specifically as after-treatment agents for damaged hair. In addition, the hair treatment agents themselves, such as the fixatives as part of a permanent wave treatment or the colorants, were mixed with additional care substances. For example, DE-Al-196 17 569 proposed using special amino acids as care substances.

It has now surprisingly been found that a completely new restructuring of keratin fibers can be achieved with a completely new enzymatic process.

Restructuring in the sense of the invention reduces the damage to keratin fibers caused by a wide variety of influences understand. Here, for example, the restoration of natural strength plays an important role. Examples of damaging influences are, for example, permanent wave treatments, oxidative dyeing or lightening of the flakes, as well as frequent washing, blow-drying and combing. Furthermore, damage from environmental influences, such as UV light, can occur. Restructured fibers are characterized, for example, by an improved sheen, by an improved handle and by easier combing. Furthermore, successful restructuring can be demonstrated physically as an increase in melting point compared to the damaged fiber.

A first subject of the present invention is therefore a process for restructuring keratin fibers, in which at least one enzyme of the transglutaminase type and (B) at least one active substance which has a substrate activity for the enzyme are applied to the fibers.

In addition to the restructuring effect of damaged fibers, a second aspect of the present invention is also the achievement of a hair-setting effect on undamaged hair. The method according to the invention can therefore also be used for setting the hair for special styling effects.

According to the invention, keratin fibers include furs, wool. Feathers and especially human hair understood.

An enzyme which is preferably used in the process according to the invention is transglutaminase (official name: protein-glutamine gamma-glutamyltransferase; EC 2.3.2.13). This enzyme preferably catalyzes the reaction of the amino acid residue glutamine within a protein with an alkylamine to form an N5-alkylgutamine protein with the release of ammonia. An alkylamine which is preferred in nature and which plays a role in this reaction is the amino acid lysine or the amino acid residue lysine within a protein. In principle, all enzymes with transglutaminase activity are suitable for carrying out the present invention. For example, transglutaminases obtained from guinea pig liver, Physarum pυlycephalum, Medicago sutiva or Bacillus subtilits are suitable. Calcium-independent transglutaminases, as described, for example, in EP-726 317-A2 and EP-397 606-Λ 1 and sold by Ajinomoto, are particularly preferred. Commercial products Activa * WM and EB from Ajinomoto are preferred; Activa ^* WM is particularly preferred.

The use of transglutaminases in cosmetic formulations is already known from the literature. For example, US Pat. No. 5,490,980 describes an agent for the treatment of human skin, hair or nails with which active ingredients containing a primary amine group are attached to the glutamine residues of the skin, hair or nails by means of transglutaminase. However, this document does not contain any references to the subject matter of the present invention and the restructuring properties of this method.

According to the invention, active substance with substrate activity means all substances which can be attached to the hair by means of the transglutaminase. This can be done, for example, by networking the active ingredients with substrate activity with one another, that is to say by forming a type of shell around the hair. However, this can preferably also be done by covalent bonds of the active substances with substrate activity to the lysine and / or glutamine residues of the hair.

In a first preferred embodiment of the present invention, naturally occurring substances are used as active substances with substrate activity. Proteins are particularly suitable for these purposes. Protein hydrolyzates and their derivatives. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).

According to the invention, the proteins and protein hydrolysates of both vegetable and animal origin can be used. Animal proteins are, for example, elastin, collagen, keratin, silk and milk protein. Examples of proteins of plant origin are soy, almond, pea, algae, potato and wheat protein.

Although the use of the proteins as such is preferred, other natural active substances with substrate activity, such as peptides, amino acids and corresponding derivatives, may also be used in their place. It is also possible, although less preferred, to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products or cationically derivatized.

Casein, soy protein and wheat protein are particularly preferred. Casein is very particularly preferred.

In a second preferred embodiment of the present invention, substances which are synthetically functionalized with an H ₂ NR group or an H _: N (CO) -R 'group are used as active ingredients with substrate activity, where R and R' are are an unbranched C, - to C ₈ alkylene group. Particularly preferred functional groups are the groups H ₂ N- (CH ₂ ) ₄ - and H _: N- (CO) -CH _: -CH, - derived from lysine or glutamine.

Furthermore, according to the invention, monomers, such as lysine and glutamine, can also be offered as active ingredients with substrate activity. These can be used both as an additional active ingredient with substrate activity and as the sole component. It can be preferred according to the invention to use both proteins and corresponding monomers in the process for improving the wash fastness in order to enable a dense network of the active substances with substrate activity to be built up more quickly. The active substances with substrate activity are contained in the agents used according to the invention preferably in amounts of 0.005 to 10% by weight, based on the total agent. Amounts of 0.01 to 2% by weight are particularly preferred. The mass ratio of the enzyme of the transglutaminase type to the active substance with substrate activity is preferably 1: 4000 to 1: 1, particularly preferred is a mass ratio of 1: 2000 to 1:50.

The invention is not subject to any restrictions with regard to the timing of the method. In principle, it is possible to apply two separate preparations containing (a) the active substance with substrate activity and (b) the enzyme of the transglutaminase type in succession to the fibers in any order. In a preferred embodiment, the two components (a) and (b) are applied to the fibers in this order. A separate application of the components in the order (b) (a) is also according to the invention. Here, however, there should not be too great a time interval between steps (a) and (b), so that the fibers do not dry between the steps.

Although these 2-stage processes lead to the desired effects, it can be preferred to carry out the process according to the invention in a 1-step process, since these processes are easier to use. The active substance with substrate activity can be applied together with the enzyme preparation. According to the invention, ice is preferred to mix the two components only immediately before use.

Although the enzyme preparation can in principle remain on the hair, in a preferred embodiment of the process according to the invention the preparation which contains the enzyme is rinsed out after an exposure time of 3 to 120 minutes. This rinsing can be done with pure water. Exposure times of 15 to 30 minutes have proven to be sufficient in most cases. Regardless of the course of the method according to the invention, it has proven to be advantageous to use the enzyme preparation at a temperature of 20 to 55 ° C., in particular 35 to 50 ° C.

The type of preparation of the enzyme preparation is not subject to any fundamental restrictions. Aqueous, alcoholic and oily preparations and mixtures thereof are particularly suitable according to the invention. Aqueous preparations are particularly preferred. They can be, for example, solutions, dispersions, emulsions (water in oil emulsions, oil in water emulsions and multiple emulsions and PIT emulsions). The pH of these preparations is generally 2 to 10, preferably 4 to 9 and particularly preferably 6 to 8.

In a preferred embodiment of the present invention, the enzyme preparations are formulated in the form of a thickened solution. For this purpose, the agents with thickeners such as 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. Thickened polyvinyl alcohol or polyacrylic acid polymers. The enzyme preparations are preferably formulated with low viscosity.

In addition to the enzyme and possibly the active substance with substrate activity, the enzyme preparations can contain all the usual constituents which are suitable for the treatment of keratin fibers, in particular human flakes. Aqueous preparations are preferred. In the context of the inventions, aqueous preparations are understood to mean those compositions which contain at least 50% by weight of water, based on the total composition.

It has proven to be advantageous if the enzyme preparation contains at least one surfactant. It can be both anionic, ampholytic, zwitterionic or act non-ionic surfactants as well as cationic surfactants. The person skilled in the art can check a possible influence of the various surfactants on the activity of the transglutaminase-type enzyme, if necessary 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.

In individual cases, however, it has proven to be advantageous to select the surfactants from amphoteric or nonionic surfactants, since these generally have less influence on the dyeing process according to the invention.

Suitable anionic surfactants in agents 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.

Non-ionic surfactants contain z. 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 moles of ethylene oxide and / or 0 to 5 moles 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 -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues 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'O- (Z) _χ . These connections are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1 -decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only a certain alkyl radical R '. Usually, however, these compounds are made 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 respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R 'consists essentially of C ₈ - and C, ₀ -alkyl groups, essentially of C ₁₂ - and C ₁₄ -alkyl groups, essentially of C ₈ - to C, ₆ -alkyl groups or essentially consists of C ₁₂ to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred. The alkyl polyglycosides which can be used according to the invention contain on average 1 1 to *> sugar units. Alkyl polyglycosides having \ values of 1.1 to 1.6 are preferred. Alkyl glycosides in which \ 1.1 to 1.4 are particularly preferred

In addition to their surfactant action, the alkylglycosides can also be used to improve the fragrance components on the hair. The person skilled in the art will therefore prefer that the effect of the parlumole on the hair going beyond the duration of the hair treatment is preferred use this substance class as a further ingredient of the preparations according to the invention

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

Furthermore, especially as co-surfactants, zwitterionic surfactants can be used. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ⁽ '- or -S0 ₃ ⁽ ' group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammomum glycate, for example the cocoalkyl-dimethylammonmm-glycinate, N-acyl-ammopropyl-N N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl- 3-carboxylmethyl-3-hydroxyethyl ιmιdazohne with 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate A preferred zwitteπonic surfactant is known under the INCI name Cocamidopropyl Betaine fatty acid amide deπvat

Are also suitable in particular as co-surfactants, ampholytic surfactants sub-am- pholytischen surfactants are surface-active compounds which, apart from a C ₈ -C, _s alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkyl- glycine, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _l2 _, ₈ acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the compounds known under the INCI names Quaternium-27 and Quaternium-83 compounds imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, and Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An invented According to the invention, particularly suitable compound from this group of substances is the lower part of the name Tegoamid "S 1 8 commercially available stearamidopropyl / dimethylamn

The compounds with alkylene groups used as surfactant can 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 mixtures of substances with different alkyl chain lengths depending on the respective raw material are obtained receipt

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto 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. “Normal” homolog distribution includes mixtures of Homologs understood that are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts The use of products with a narrow flomologist distribution can be preferred

Furthermore, the enzyme preparations used according to the invention preferably 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, water-soluble substances are those whose solubility in water at 20 ° C. is less than 0.1% by weight. The melting point of the individual 01- or Fat components are preferably below about 40 ° C. 01 and fat components which can be liquid at room temperature, ie below 25 ° C. Be particularly preferred according to the invention. When using several oil and fat components as well as paratfins and waxes, it is usually also sufficient if the mixture of oil and oil components and, if necessary, pai atfins and waxes satisfies these conditions

A preferred group of oil components are vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojobaol, orange oil, wheat germ oil, peach kernel oil and the liquid components of coconut oil

However, other Tπglyceπdole such as the liquid portions of beef tallow and synthetic Tπglyceπdole are suitable

Another particularly preferred group of compounds which can be used as an oil component according to the invention are liquid paraffinols and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n- octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, 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 as well as di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n- octyl ether and 2-methyl-pentyl-n-octyl ether The compounds available as commercial products 1 3-Dι- (2-ethyl-hexyl) -cyclohe \ an (Cetiol "S) and Di-n-octvlethei (Cetiol" OE) can be preferred his

synthese oder der Dimerisierung von ungesättigten Fettsäuren anfallen, mit Alkoholen wie beispielsweise Isopropylalkohol, Capronalkohol, Caprylalkohol, 2-Ethylhcxylal- kohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol. Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol. Petroselinylalkohol, Linolylalkohol. Linolenyialkohol, Elaeostearylalkohol, Arachylal- kohol, Gadoleylalkohol, Behenylalkohol. Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z. B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxo- synthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Erfindungsgemäß besonders bevorzugt sind Isopropylmyristat, Isononan- säure-C 16-18-alkylester (Cetiol^® SN), Stearinsäure-2-ethylhexylester (Cetiof 868). Cetyloleat, Glycerintricaprylat, Kokosfettalkohol-caprinat/-caprylat und n-Butylstearat.Oil components which can likewise be used according to the invention are fatty acid and fatty alcohol esters. The monoesters of fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances involves the products of esterification of fatty acids with 8 to 24 carbon atoms, such as, for example, caproic acid. Caprylsauie. 2-Efhv l-hexane acid, Capπnsaure, Laurmsaure, Isotπdecansaure, Myπstmsaure, Palmitmsaure Palmoleinsaure. Stearic acid. Isostearic acid, oleic acid, elaidic acid, petrosine acid. Linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadolinic acid, behenic acid and erucic acid as well as their technical mixtures, which are used, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's

Synthesis or dimerization of unsaturated fatty acids are obtained with alcohols such as isopropyl alcohol, capron 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. Linolenial alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol. Erucyl alcohol and brassidyl alcohol and their technical mixtures, the z. B. in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention particularly preferably isopropyl myristate, isononanoic acid C 16-18 alkyl ester (Cetiol ^® SN), stearic acid-2-ethylhexyl ester (Cetiof 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 are also suitable. 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 are oil components which can be used according to the invention. B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used as oil components acting according to the invention. The fatty alcohols can be saturated or unsaturated and linear or branched. For example, decanol, octanol, octenol, dodecenol can be used for the purposes of the invention. üecenol, octadienol, dodecadienol. Decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol. Caprinal alcohol, linoleyl alcohol, linolenial alcohol and behenyl alcohol. as well as their Guerbet alcohols, this list being intended to be exemplary and not limiting. However, the fatty alcohols derive from preferably natural fatty acids, usually from a recovery from the esters of the fatty acids Reduction can be assumed according to the invention. Those fatty alcohol cuts that are produced by reducing naturally occurring triglycerides such as beef tallow, palmol, peanut oil, rubole, cottonseedol, soybean oil, sunflower oil and linseed oil or fatty acid esters resulting from their transesterification products with corresponding alcohols can also be used, and thus a mixture of different fatty alcohols

According to a preferred embodiment, the enzyme preparations used according to the invention contain a care substance. This care substance is preferably selected from cationic polymers and silicones

A first group of cationic polymers are the so-called "temporarily cationic" polymers. These polymers usually contain an amino group which is present as a quaternary ammonium group at certain pH values and is therefore cationic.

However, the permanent cationic polymers are preferred among the cationic polymers. According to the invention, "permanently cationic" refers to those polymers which have a cationic group regardless of the pH of the agent. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose -Deπvate, as they 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 Commercially available products Q2-7224 (manufacturer - Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 emulsion (containing a hydroxyl-ammo-modified silicone, which is also referred to as amodimefhicone), SM-2059 (manufacturer general Electric), SLM-55067 (manufacturer Wacker) and Abil ^® -Öuat 3270 and 3272 (manufacturer ller: Th Goldschmidt, diquaternary polydimethylsiloxanes, Ouaternιum-80), Cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ^® Guar and Jaguar *,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^Ä 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino alkyl acrylate and methacrylate. such as vinyl pyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially, vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as the under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Likewise used as cationic polymers are those under the names Polyquaternium-24 (commercial product e.g. Quatrisoft * LM 200), Polyquaternium-32, Polyquaternium-35 and Polyquaternium-37 (commercial products e.g. Salcare ^® SC 92 and Salcare ^® SC 95) known polymers. Also usable in the invention are the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ^® VC 713 (manufactured by ISP). Gafquat ^® ASCP 101 1, Gafquat ^® HS 1 10, 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 copo- polymers and polymers of the type polyquaternium-2. Cationic cellulose derivatives, in particular the Flandels product Polymer * JR 400, and polymers of the type Polyquaternium-2, in particular the commercial product Mirapol * A-1 5, are very particularly preferred cationic polymers.

The cationic polymers are contained in the agents used according to the invention preferably in amounts of 0.05 to 10% by weight, based on the total agent. Quantities from 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 are amphoteric polymers, ie polymers that contain both free amino groups and free - COOH or S0 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 ,, - groups, and summarized those polymers which contain -COOH- or SO-, H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (l, l, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group Acrvlsäure, 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 for example in German Laid-open specification 39 29 973 and the state of the art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, 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, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethyl polysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200 and DC 1401 and the commercial products DC 344 and DC 345 from Dow Corning. Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Do Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM -55067 (manufacturer: Wacker) as well as Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80) and the commercial product Fancorsil ^® LIM-1. The product Dow Corning ^® 1784 is a suitable anionic silicone oil.

In addition to the enzyme of the transglutaminase type and the other preferred components mentioned above, the enzyme preparations can in principle contain all further components known to those skilled in the art for such cosmetic products.

Other active ingredients, auxiliaries and additives are, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,

Structurants such as maleic acid, lactic acid and amino acids hair conditioning compounds such as phospholipids, such as soybean lecithin. Egg lecithin and cephaline,

Perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, active ingredients that improve fiber structure, in particular panthenol and mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l alkylamidoethyl-2-alkylimidazolinium methosulfate defoamers such as silicones, dyes 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 customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those from groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as green tea extracts. 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, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root. Cholesterol,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerin, propylene glycol monoethyl ether. Carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, pigments,

Stabilizing agent for hydrogen peroxide and other oxidizing agents, blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, C0 ₂ and air.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant ones known to the person skilled in the art Manuals, e.g. B. Kh. Schrader. Basics and formulations of cosmetics, 2 edition. Hüthig Buch Verlag, Heidelberg. 1989.

A second subject of the invention is the use of (A) at least one enzyme of the transglutaminase type and (B) at least one active ingredient which has a substrate activity for the enzyme for the restructuring of keratin fibers.

A third subject of the invention is the use of (A) at least one enzyme of the transglutaminase type and (B) at least one active ingredient which has a substrate activity for the enzyme for strengthening keratin fibers.

A fourth object of the present invention is a two-part kit for restructuring keratin fibers, which contains a first preparation containing one (a) an active substance with substrate activity and a second composition containing (b) an enzyme of the transglutaminase type.

The following examples are intended to explain the invention in more detail.

Examples

a) Pretreatment

Strands from Alkinco (0.5 g, code 6634) were subjected to conventional permanent wave treatments with the commercial product Poly Lock-Normal permanent wave. As part of this permanent wave treatment, the fibers were exposed to the reducing solution (containing 7.9% by weight thioglycolic acid) in a first step for 40 minutes at room temperature, rinsed with pure water and then fixed at room temperature for 10 minutes (oxidation solution containing 2.6 % By weight hydrogen peroxide). After the oxidative treatment, the fibers were rinsed and dried.

b) post-treatment

Experiment 1) Aftertreatment According to the Invention

The strands were each at a temperature of 50 ° C. for 60 minutes in 2 ml of an aqueous casein solution (30 mg / ml, with tris (hydroxymethyl) aminomethane (TRIS) -HC1-

Buffer adjusted to pH 7.6) with 100 μl of an aqueous transglutaminase solution

(50 mg / ml Activa ^® WM ¹ , corresponding to 0.5 mg / ml active substance; adjusted to pH 7.6 with TRIS-HCl buffer) was immersed.

¹ powdered commercial product. 1 wt% transglutaminase in 99 wt% dextrin

Experiment 2) Post-treatment with casein

The strands were each immersed at 50 ° C. for 60 minutes in 2 ml of an aqueous casein solution (30 mg / ml, adjusted to pH 7.6 with tris (hydroxymethyl) aminomethane (TRIS) -HC1 buffer).

Experiment 3) Post-treatment with transglutaminase

The tresses were each ml at a temperature of 50 ° C for 60 minutes in 2 an aqueous transglutaminase solution (l, 2 mg / ml Activation ^® WM corresponding to 0,012mg / ml active substance, with TRIS-FICL buffer at pH 7.6 adjusted) immersed , c) Evidence of the hair structuring effect using HP-DSC

The following melting points were determined by means of a DSC analysis (Perkin Elmer DSC-7):

A statistical evaluation after a two-sided heterogeneous T-test showed a significance of 99.73% between the measured values of tests 1) and 2).

Claims

claims 1 . Process for restructuring keratin fibers, characterized in that on the fibers (A) at least one transglutaminase type enzyme and (B) at least one active ingredient which has a substrate activity for the enzyme can be applied. 2. The method according to claim 1, characterized in that the enzyme is a calcium-independent transglutaminase. 3. The method according to any one of claims 1 or 2, characterized in that the active substance with substrate activity is a protein or a protein hydrolyzate. 4. The method according to claim 3, characterized in that the active ingredient with substrate activity is selected from casein, soy protein and wheat protein. 5. The method according to any one of claims 1 or 2, characterized in that the active substance with substrate activity is a synthetic functionalized with an H ₂ NR group or an H ₂ N- (CO) -R 'group, wherein R and R 'stand for an unbranched C, - to C ₈ alkylene group. 6. The method according to claim 5, characterized in that the active substance with substrate activity carries at least one H ₂ N- (CH,) group. 7. The method according to claim 5, characterized in that the active substance with substrate activity carries at least one H _: N- (CO) -CH ₂ -CH ₂ group. 8. The method according to any one of claims 1 to 7, characterized in that the enzyme preparation is applied to the fibers together with the active ingredient with substrate activity. 9. The method according to any one of claims 1 to 8, characterized in that the exposure time is 3 to 120 minutes. 10. Use of (A) at least one enzyme of the transglutaminase type and (B) at least one active ingredient which has a substrate activity for the enzyme for the restructuring of keratin fibers. 1 1. Use of (A) at least one enzyme of the yp of transglutaminase and (B) at least one active ingredient which has a substrate activity for the enzyme for the strengthening of keratin fibers. 12. Two-part kit for restructuring keratin fibers, characterized in that it contains (a) a composition containing an active ingredient with substrate activity, and (b) a composition containing an enzyme of the transglutaminase type.