WO2002043678A2 - Enzymatic fixation of derivatised carbohydrates to fibrous materials - Google Patents

Abstract

The invention relates to a method for the enzymatic fixation of derivatised carbohydrates to fibrous, in particular keratinous materials, such as hair or wool, to a multi-component system comprising at least one carbohydrate derivative and one enzyme and to the use thereof for influencing the characteristics of fibrous materials, in particular the characteristics of hair, such as volume, shine, hold, body, tactility, electrostatic charge and resistance to heat, UV and IR radiation.

Description

 Enzymatic fixation of derivatized carbohydrates to fibrous

materials

The invention relates to a method for the enzymatic fixation of. derivatized carbohydrates on fibrous, in particular keratinous materials, such as hair or wool, a multicomponent system comprising at least one carbohydrate derivative and an enzyme, and its use for influencing the properties of fibrous materials, in particular the properties of hair such as volume, shine, hold, fullness, tactility , Electrostatics and resistance to heat, UV and IR radiation.

The cleaning and care of the hair is an important part of human body care. Both cleaning the hair with shampoos and decorating the hairstyle, for example by dyeing or perming, are interventions that influence the natural structure and properties of the hair. After such a treatment, for example, the wet and dry combability, hold, fullness, shine and tactility of the hair can be unsatisfactory. In addition, the hair is damaged by environmental influences such as UV, IR radiation and heat, e.g. B. by blow drying the hair.

To maintain and restore the aforementioned properties, it has therefore long been customary to subject the hair to a special after-treatment. The hair, usually in the form of a rinse, is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, combability, hold, fullness, shine and feel of the hair are improved. For the temporary influencing 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 and alkyl cellulose in WO-A-97/38673 , US-A-5,534,247 and WO-A-94/06410. Furthermore, smaller carbohydrate components such as glucose in WO-A-95/00104, maltose in WO-A-95/00104 and lactose in DE-A-19610458 are also used. When applying such rinses, however, only remains a relatively small proportion of the active ingredients at their place of action. The majority is rinsed off immediately or detached from the hair surface by later washing the hair or mechanical stress, such as combing.

US-A-3,619,114 teaches the permanent modification of keratinous substrates by copolymerization with vinyl monomers in the presence of free radical catalysts and subsequent treatment with aqueous ammoniacal copper hydroxide solutions. Due to the toxicity of the compounds used, the application is limited to inanimate keratin fibers. US-A-2, 615,782 teaches the modification of keratinous fibers by forming disulfide bridges between hair and active substance. Another method for fixing compounds which serve to permanently shape hair and which is particularly aimed at permanent wave processes is the use of so-called colored salt derivatives, as described in DE-A-3735086, DE-A-4109869 and EP-A- 0246151. US-A-3,415,606 teaches the use of reactive dyes which have a long-term effect on the hair.

It is therefore of urgent interest to fix protective, restorative and restructuring agents preferably permanently on the hair and at the same time to avoid polluting the environment and harming the health of the user.

The object is achieved according to the invention by a method in which a fibrous, keratinous material is treated with at least one carbohydrate derivative and an enzyme.

In particular, the invention relates to a method for the enzymatic fixation of derivatized carbohydrates on fibrous, keratinous materials by their treatment with

at least one carbohydrate derivative (component A) according to the following formula (I),

[ZYRX] _n , (I), in which

Z is a carbohydrate residue,

Y is an amino, thioether, amide, ester or ether group, the group R

a linear or branched, saturated or unsaturated, aliphatic or alicyclic hydrocarbon radical having 1 to 12 carbon atoms, which may be substituted with an ester group -COOR ', in which R ^{' is} a -C 1 -C ₂ -alkyl radical,

- a single bond,

- An arylene, -CC ₄ alkylene-arylene or C ₂ -C ₆ -alkenylene-arylene group with 5 to 12 carbon atoms in the arylene radical, which may optionally be substituted with -C ~ C ₆ -alkyl and / or C ₂ -C ₆ alkoxy groups, or

- A heteroarylene, -CC alkylene heteroarylene or C ₂ -C ₆ alkenylene heteroarylene group with 3 to 8 carbon atoms in the heteroarylene radical and one or two heteroatoms (s) selected from N, O and S, which are substituted can be with C ₁ -C ₆ alkyl and / or C ₂ -C ₆ alkoxy groups, the alkylene, arylene and heteroarylene group in R optionally having at least one oxo, formyl, Ci-Cs acyl - or Cβ-Cio-aryloyl group can be substituted, n = 1 or 2 and X is a thiol group (-SH) for n = 1 and a thioether group (-S-) for n = 2,

- In combination with an enzyme (component B), for which component A has substrate activity.

It is assumed that the carbohydrate derivatives are enzymatically bound to functional groups of the keratin fibers when they are used, and that this chemical linkage means that the active ingredient remains on the fiber even after washing or under mechanical stresses and has a long-lasting, preferably permanent effect there. This concept can be used with numerous fibrous materials, but preferably with natural and synthetic fibers such as textiles, fleeces (non-wovens), leather, fur and particularly preferred for keratin fibers such as wool and hair.

The carbohydrate residue Z in formula (I) can be cyclic or open-chain and has an average molecular weight of up to 1000, preferably up to 400. For the purposes of the present invention, a carbohydrate residue is a residue which results from a carbohydrate in that either a hydroxyl group of the carbohydrate is removed, or an amino group of the carbohydrate is removed, if the carbohydrate contains one. Preferred carbohydrates, from which the carbohydrate residues Z are derived, are selected from the group consisting of aldohexoses, aldopentoses, aldofuranoses, aldopyranoses, glycosamines of aldopyranoses, dimeric reducing aldopyranoses and the glycosamines, dimeric reducing aldofuranoses formed therefrom and the glycerol carbons formed therefrom, and the resulting glycosene carbons , Glycuronic acids, aldonic acids or the lactones formed therefrom. Carbohydrates which are selected from the group consisting of allose, old rose, galactose, glucose, gulose, idose, mannose, talose, glucosamine, galactosamine, mannosamine, maltose, cellobiose, gentiobiose, lactose, lactosamine, melezitose are particularly suitable in the context of the invention , Panose, erythrose, threose, ribose, arabinose, xylose, lyxose, glucuronic acid, gluconic acid and gluconic acid-δ-lactone, D-erythronic acid-γ-lactone, D-ribonic acid γ-lactone, D-xylonic acid γ-lactone, D -Gulonic acid-γ-lactone, L-gulonic acid-γ-lactone, L-mannonic acid-γ-lactone, α, D-glucoheptanoic acid-γ-lactone and α, ß-

Glucooctansäure-γ-lactone.

The pyranoses can be derivatized to form the Z-Y-R bonds by methods known in the art at positions 1 (anomeric center) and / or 6, and those of furanoses at positions 1 or 5.

Suitable compounds for the preparation of the carbohydrate derivatives (I) by derivatizing carbohydrates are compounds of the formula HY-RX, where Y, R and X have the meanings given above. For n = 2, X is present as a capped thiol in the form of the disulfide HY-RSSR-YH. Exemplary Aminothiols, such as 2-aminoethanethiol, 1-amino-2-methyl-2-propanethiol, cysteine methyl ester, cysteine ethyl ester, thiocytosine, 2-aminothiophenol, 4-aminothiophenol, 2-amino-5-mercapto-1, 3,4 thiadiazole, 3- Amino-5-mercapto-1, 2,4 triazole, dithiols such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol , 1,8-octanedithiol, 2-mercaptoethyl sulfide, 1,2-benzendimethanethiol, 1,3-benzendimethanethiol, 1,4-benzendimethanethiol, dimercaptobenzene, or diaminodisulfides such as bis- (4-aminophenyl) disulfide, cystamine, cystine dimethyl ester, cystine diethyl Bis- (5-amino-2-pyridyl) disulfide, dithiobis- (l-amino-naphthalene), bis- (2-amino-p-tolyl) disulfide, can be used to prepare the carbohydrate derivatives (I).

In one embodiment of the invention, the group R can be a hydrocarbon group having 1 to 12, preferably 2 to 8, particularly preferably 2 to 6 carbon atoms. Preferred alkylene groups are the methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, pentylene, hexylene and cyclohexylene group. In a particularly preferred embodiment, the group R represents an alkylene group substituted with an ester group, such as, for example, methoxycarbonyl-ethyl, ethoxycarbonyl-ethyl, n-propoxycarbonyl-ethyl, iso-propoxycarbonyl-ethyl, n-butoxycarbonyl-ethyl , iso-butoxycarbonyl-ethyl or t-butoxycarbonyl-ethyl group. Alternatively, arylene, C ₁ -C ₄ -alkylene-arylene or C ₂ -C ₆ -alkenylene-arylene groups with 5 to 12, preferably 6 to 10, particularly preferably 6 carbon atoms in the arylene radical, which are optionally substituted, can be used for R can be with -CC ₆ alkyl, and / or C ₂ -C ₆ alkoxy groups, such as in particular groups which are derived from the phenyl, biphenyl, naphthyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl -, phenylvinyl-, cinnamyl-, phenylallyl-, methylphenyl-, ethylphenyl-, propylphenyl-, iso-propylphenyl-, butylphenyl-, iso-butylphenyl-, tert-butylphenyl-, methoxyphenyl-, ethoxyphenyl- propoxyphenyl-, iso-propoxyphenyl- , Butoxyphenyl, iso-butoxyphenyl and tert-butoxyphenyl group.

In a further alternative, the radical R can be a heteroarylene, -CC ₄ -alkylene-heteroarylene or C ₂ -C ₆ -alkenylene-heteroarylene group having 3 to 8, preferably 3 to 6, particularly preferably 3 to 5 carbon atoms in the Heteroarylene residue and one or two hetero atom (s) be selected from N, O and S, which may additionally be substituted with Cι-C ₆ alkyl and / or C ₂ -C ₆ alkoxy groups. Suitable heteroaryl groups are derived in particular from the pyridyl, pyrimidyl, pyridazyl, pyrazyol, furanyl, thiophenyl, oxazolyl, isooxazolyl, thioazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinazolinyl, pyridyl Pyridylethyl-, pyridylpropyl-, pyridylbutyl-, pyrimidylmethyl-, pyrimidylethyl-, pyrimidylpropyl- pyrimidylbutyl-, pyridazylmethyl-, pyridazylethyl-, pyridazylpropyl-, pyridazylbutyl- pyrazylmethyl- pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl-, pyrazylpyl- , Furanylbutyl-, Thiophenylmethyl-, Thiophenylethyl- Thiophenylpropyl-, Thiophenylbutyl-, Oxazolylmethyl-, Oxazolylethyl- Oxazolylpropyl-, Oxazolylbutyl-, Isooxazolylmethyl-, Isooxazolylethyl- Isooxazolylpropyl-, Isooxazolylbutyl-, Thioazolylmethyl-, Thioazolylethyl- Thioazolylpropyl-, Thioazolylbutyl-, Quinolinylmethyl- , Quinolinylethyl- Quinolinylpropyl-, Quinolinylbutyl-, Isoquinolinylmethyl-, Isoquinolinylethyl- Isoquinolinypropyl-, Isoquinolinylbutyl-, Pht halazinylmethyl-, phthalazinylethyl- phthalazinylpropyl-, phthalazinylbutyl-, quinazolinylmethyl, quinazolinylethyl quinazolinylpropyl, quinazolinylbutyl, pyridylvinyl, pyridylallyl, pyrimidylvinyl pyrimidylallyl, pyridazylvinyl-, pyridazylvinyl-, pyridazylvinyl-, pyridazyl- vinyll Oxazolylallyl-, isooxazolylvinyl-, isooxazolallyl-, thioazolylvinyl-, thioazolylallyl- quinolinylvinyl-, quinolinylallyl-, isoquinolinylvinyl-, isoquinolinylallyl- phthalazinylvinyl-, phthalazinylallyl-, quinazolinylvinyl-, methyl-pyrid- , -furanyl-, -thiophenyl-, -oxazolyl-, -isooxazolyl-, -thioazolyl-, ethoxypyridyl-, -pyrimidyl-, -pyridazyl-, -pyrazyl-, - furanyl-, -thiophenyl-, -oxazolyl-, -isooxazolyl -, -thioazolyl-, propoxypyridyl-, - pyrimidyl-, -pyridazyl-, -pyrazyl-, -furanyl-, -thiophenyl-, -oxazolyl-, -isooxazolyl-, - thioazolyl-, iso-propoxypyridyl-, -pyrimidyl-, -p yridazyl-, -pyrazyl-, -furanyl-, - thiophenyl-, -oxazolyl-, -isooxazolyl-, -thioazolyl-, butoxypyridyl-, -pyrimidyl-, - pyridazyl-, -pyrazyl-, -furanyl-, -thiophenyl-, -oxazolyl-, -isooxazolyl-, -thioazolyl-, iso-butoxypyridyl-, -pyrimidyl-, -pyridazyl-, -pyrazyl-, -furanyl-, -thiophenyl-, - oxazolyl-, -isooxazolyl-, -thioazolyl-, tert .-Butoxypyridyl, -pyrimidyl, -pyridazyl, -pyrazyl, -furanyl, -thiophenyl, -oxazolyl, -isooxazolyl, -thioazolyl group. For example, compounds (anomer or mixture of anomers) according to the following formulas (II) and (III) [bis (N- (4-phenyl-β-D-glucopyranosyl) propionic acid amido) disulfide, Olaf Ramström, Jean-Marie Lehn Chembiochem 2000, 1, 41-48] and / or in the case of (II) whose hydrohalides are used:

(II)

(III)

Enzymes, preferably protein disulfide isomerase (PDI), for which component A of the method has substrate activity and which can preferably bring about a linkage of the carbohydrate derivatives with functional groups of the fibrous, keratinic materials act as component B in the process according to the invention. U (unit) is the amount of enzyme that 1 unit of unfolded ribonuclease can fold (reactivate) within one minute at pH 7.5 and 30 ° C. According to the invention, 0.1 to 2000, preferably 500 to 1500, units of enzyme (e.g. PDI) can be used. PDI rearranges intra- and intermolecular disulfide bridges in proteins. Protein disulfide isomerase belongs to the main group of isomerases and has the EC number 5.3.4.1 (The classification of enzymes is recommended by the "Nomenclature Committee of the International Union of Biochemistry and Molecular Biology" (IUBMB) and classifies all enzymes for which an EC (IUBMB Enzyme Committee) number is assigned. With regard to the time sequence, the method according to the invention can be carried out in different variants. In principle, it is possible to apply component A with substrate activity and the enzyme as component B to the fibrous material in succession in any order. In a preferred embodiment, component A and component B are applied to the fibrous material in this order. An application of the components in the order first B, then A is also according to the invention.

Although these two-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 such a process is easier to use. Component A is preferably mixed with component B immediately before use, and the mixture is then applied to the fibrous material in a single step.

Although the mixture can in principle remain on the fibrous material, in a preferred embodiment of the method according to the invention it 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 process according to the invention, it has proven to be advantageous to use the enzyme at a temperature of 20 to 55 ° C., in particular 35 to 50 ° C.

It is preferred if in the process according to the invention component A and component B are each used in the form of a preparation which, in addition to components A and B, comprises a carrier. In addition to component A with substrate activity or in addition to the enzyme as component B, the preparations can contain all customary constituents which are suitable for the treatment of fibrous materials, in particular keratin fibers, and particularly preferably human hair. suitable Preparations are solid, liquid, gel-like or pasty and preferably consist of aqueous systems. The preparations which can be used according to the invention can be formulated as a solution, lotion, emulsion, microemulsion, cream or gel.

The further constituents of the preparations used according to the invention essentially depend on the type of fibrous material treated and can be suitably selected by the person skilled in the art.

The preparation is particularly preferably a hair treatment agent. In principle, the preparations used according to the invention include all known types of hair treatment agents, such as Hair shampoos, hair rinses, hair conditioners, hair treatments, hair fixers, hair sprays, blow-dry waves, permanent waving agents and hair colorants. Hair treatments and hair conditioning agents, in particular those agents which are applied to the hair in the morning in order to give it a certain degree of firmness for the rest of the day, and hair shampoos are preferred forms of the agents according to the invention.

Depending on the type of hair treatment composition, the preparations according to the invention can contain all active ingredients, additives and auxiliaries known in such compositions. In many cases, the preparations contain at least one surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases it has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

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 or ether and amide groups and hydroxyl groups may be included. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 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 C- Atoms in the acyl group, acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 up 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, methyl alpha-sulfofatty acid 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 2-15 molecules of ethylene oxide and / or propylene oxide to 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. Non-ionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Such connections are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles

Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the

alkyl group,

Cι ₂ -C ₂₂ fatty acid monoesters and diesters of addition products from 1 to 30

Mole of ethylene oxide to glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well

- 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 RO- (Z ') _x . These connections are characterized by the following parameters.

The alkyl radical R 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 Cs and Cio alkyl groups, essentially from C ₂ and Cu alkyl groups, essentially from Cs-Ciβ alkyl groups or essentially from C ₂ -C ₆ -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 an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to 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, zwitterionic surfactants can be used, in particular as co-surfactants. Such surfactants are used as zwitterionic surfactants. Designates bonds that carry 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-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a Cs-Cis-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-alkylglycines, N-alkylpropionic acids, N-alkylamino-butyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acylaminoethyl aminopropionate and C12-18 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, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distea- ryldimethylammonium 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 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) dimethyl-ammonium chloride, as well as 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 inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

Also suitable according to the invention are 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 hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxanes, Quatemium-80). An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

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

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 is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. 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 homolog distribution can be preferred.

The surfactants in the preparations according to the invention are usually in amounts of 0.1 to 65% by weight, preferably in amounts of 2 to 50% by weight and very particularly preferably in amounts of 8 to 20% by weight, based on the entire preparations. Nonionic surfactants are preferably present in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 5% by weight.

Furthermore, the preparations according to the invention can preferably also contain a conditioning active ingredient selected from the group consisting of cationic Surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the names Merquat ^® 100

(Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldialylammonium chloride-acrylamide copolymer) and Merquat ^® 280

(Dimethyldiallylammonium chloride-acrylic acid copolymer commercially available are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are among the names Gafaf ^® 734 and Gafquat ^® 755 are commercially available.

Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain. Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

As an alternative to the cationic polymers, zwitterionic or ampholytic polymers are particularly preferably used as conditioning agents. Preferred representatives are octylacrylamide / methyl methacrylate / tert.

Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and especially the acrylamidopropyl-trimethylammonium chloride / acrylate copolymer.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 products sold and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), 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).

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

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, cross-linked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl tert-acrylate. butyl acrylamide terpolymers,

- Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextran, cellulose derivatives, eg. 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 hydrocoloids such as polyvinyl alcohol,

Structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example

Soy lecithin, egg lecithin and cephaline,

Protein hydrolyzates, especially 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 intermediates such as ethanol, isopropanol, ethylene glycol,

Propylene glycol, glycerin and diethylene glycol, active substances that improve fiber structure, in particular mono-, di- and

Oligosaccharides such as glucose, galactose, fructose,

Fructose and lactose,

- Quaternized amines such as methyl 1-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, 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 |} 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, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, 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, β-alaninediacetic acid and phosphonic acids,

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. B. K. Schrader, Fundamentals and Formulations of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

In addition to cosmetic hair care products such as shampoos, conditioners, rinses, aerosols and gels, the preparations according to the invention can also be agents for textile or leather treatment in the form of detergents, fabric softeners and finishes.

In the preparations used in the process according to the invention, component A is present in a total 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 amount of preparation, before. The enzyme component B is used in the unit amount specified above.

A permanent influence on the properties of the treated fibrous material, in particular human hair, can be achieved by the method according to the invention, in particular an improvement of wet and dry combability, hold, moisture, strength, fullness, shine, tactility and electrostatic properties as well as resistance to UV and IR radiation and exposure to heat. The invention is particularly suitable for increasing the hair volume and for improving the hair structure. The structure-improving effect of the method according to the invention on the hair keratin can be determined quantitatively by tear measurements. These effects are particularly striking when treating heavily damaged hair using the method according to the invention. Such heavily damaged hair is created in particular by oxidizing or reducing treatment processes, e.g. B. when coloring the hair with oxidation colorants, when bleaching the hair with oxidizing agents or when deforming, z. B. when perming or straightening the hair with strong keratin reducing agents, e.g. B. with thioglycolate salts or with sulfites.

In a preferred embodiment of the invention, components A and B, each optionally in the form of preparations which contain further constituents as described above, for example in mixed, dissolved, dispersed or emulsified form, are provided separately from one another in a kit of parts ,

The invention thus furthermore relates to a kit for use in the process according to the invention for the treatment of fibrous materials, in particular human hair, which consists of the following separately packaged components: - A component A with substrate activity, as described above, preferably in the form of a preparation which additionally comprises a carrier

an enzyme B, as described above, preferably in the form of a preparation which additionally comprises a carrier.

The invention also relates to the use of a kit according to the invention in a method for treating fibrous materials, in particular human hair.

The invention further relates to the use of (a) at least one enzyme of the protein disulfide isomerase type and (B) at least one substance which has a substrate activity for the enzyme for the treatment of fibrous materials. The fibrous materials are preferably keratin fibers and particularly preferably human hair. In a further preferred embodiment, the treatment serves for restructuring, strengthening or increasing the volume of keratin fibers.

The invention is explained in more detail by the following examples, but without restricting it thereto.

Examples

1. Components A according to formula (I)

1.1 di- (N-glucosyl-4-aminophenyl) disulfide (II)

3.0 g of bis (4-aminophenyl) disulfide were dissolved in 10 ml of ethanol and added to a suspension of 1.80 g of anhydrous glucose in 10 ml of ethanol. The reaction mixture was refluxed for 4 hours and cooled to room temperature after the reaction was complete. The reaction product was converted into the crystalline hydrochloride of the compound of the formula (II) by adding hydrochloric acid. After the solid had been suctioned off, it was washed with cold methanol. TLC: R _f (free amine) = 0.37 (silica gel 60 F ₂₅ on plastic film, Merck; acetone: H ₂ 0 = 98: 2 V / V).

1.2. N, N'-di-gluconoyl-cystine dimethyl ester

3.41 g of cystine dimethyl ester dihydrochloride were taken up in anhydrous methanol, an equimolar amount of sodium methoxide was added to release the amine, and the mixture was then added dropwise to a methanolic solution of 3.56 g of δ-gluconolactone within 30 minutes. The reaction mixture was stirred at 20 ° C for 15 h and then cooled to 4 ° C. At this temperature, the N, N ^'-di- gluconoyl-cystine dimethyl ester crystallized as a beige-white-solid. After the precipitation had ended, the product was washed with cold methanol and dried in vacuo. TLC: R _f = 0.56 (acetone / water = 9: 1 V / V) mp: 168.4 - 172.2 ° C

1.3. N, N'-di-gluconoyl-cystamid

2.25 g of cystamine dihydrochloride were taken up in anhydrous methanol, an equimolar amount of sodium methoxide was added to release the amine, and the mixture was then added dropwise to a methanolic solution of 3.56 g of δ-gluconolactone within 30 minutes. The reaction mixture was heated to 60 ° C. for 24 hours and then cooled to 4 ° C., the N, N'-di-gluconoyl-cystamide precipitating out as a white solid. This was filtered off, washed with methanol and then dried in vacuo.

TLC: R _f = 0.16 (silica gel 60 F ₂₅ on plastic film, Merck company, acetone / water = 9: 1 V / V) mp: 183.1-186.4 ° C

2. Application example

To demonstrate the effects according to the invention, a two-component system according to the invention was tested on cold-waved, dark brown, Central European individual hairs which had previously been subjected to a cold wave process. For this purpose, preparations A and B listed in the following table were first prepared, which together represent a two-component system or a kit of parts consisting of two components in the sense of the invention. Ingredient amount [% by weight]

Preparation A

Compound according to formula (II) 2.0

Cetearyl alcohol 5.5

Ceteareth-20 (co-emulsifier) 2.0

Sodium laureth sulfate (surfactant) ^* 1.5

Polyquaternium-10 (cationic polymer) 0.8

Cocoamidopropyl betaine 0.5

Monoethanolamine ad pH 7

Aqua ad 100.0

Preparation B

Protein disulfide isomerase (PDI) ** 10000 units

Acrylate copolymer 0.5

Sodium laureth sulfate ^* 0.3

Buffer substances (citric acid) q.s.

Phosphate buffer ad pH 7.4

Aqua ad 100.0

^* Instead of the anionic surfactant, it is also possible to use cationic or nonionic surfactants (nonionic surfactants) such as, for example, alkyl polyglycosides (APG).

** The protein disulfide isomerase (PDI) from beef liver used is commercially available.

After the mixing of preparations A and B, the mixture was applied directly to the cold-waved hair and washed out after a contact time of 20 minutes and rinsed thoroughly. The properties of the hair were examined before and after application and compared with one another.

To demonstrate the effects according to the invention, with the aid of a Diastron MTT 670, stress values, gradients, elastic moduli and working values were used a 1% stretch of wet hair and the hair cross-section determined (tensile strain measurements). A significant strengthening of the hair could be concluded from the measurement parameters.

In addition, the hair strands were examined after conditioning under standardized, air-conditioned conditions by an expert panel with regard to sensory properties against hair treated with water ("sensory assessment"). A noticeable improvement in grip, gloss and combability was found on the hair treated by the process according to the invention.

Claims

claims 1. Process for the enzymatic fixation of derivatized carbohydrates on fibrous, keratinous materials by treating them with - at least one carbohydrate derivative (component A) according to the following formula (I), [ZYRX] _n , (I) where Z is a carbohydrate residue, Y is an amino, thioether, amide, ester or ether group, the group R a linear or branched, saturated or unsaturated, aliphatic or alicyclic hydrocarbon radical having 1 to 12 carbon atoms, which may be substituted with an ester group -COOR ^' , in which R ^{' is} a -C 1 -C ₂ -alkyl radical, - a single bond, - An arylene, -CC-alkylene-arylene or C ₂ -C ₆ -alkenylene-arylene group with 5 to 12 carbon atoms in the arylene radical, which may optionally be substituted with -CC ₆ -alkyl and / or C. ₂ - C ₆ alkoxy groups, or - A heteroarylene, C ₁ -C ₄ -alkylene-heteroarylene or C ₂ -C ₆ -alkenyl-en-heteroarylene group with 3 to 8 carbon atoms in the heteroarylene radical and one or two heteroatoms (s) selected from N, O and S. , which can be substituted with -CC ₆ -alkyl and / or C ₂ -C ₆ -alkoxy groups, the alkylene, arylene and heteroarylene group in R optionally having at least one oxo, formyl, C- ι-C ₈ -acyl or C ₆ -Cιo-aryloyl group can be substituted, n = 1 or 2 and X is a thiol group (-SH) for n = 1 and a thioether group (-S-) for n = 2, - in combination with an enzyme (component B), for which component A has substrate activity. 2. The method according to claim 1, characterized in that the enzyme used as component B is a protein disulfide isomerase. 3. The method according to any one of claims 1 or 2, characterized in that the fibrous materials are selected from the group consisting of textiles, nonwovens (non-wovens), leather, fur, wool and hair. 4. The method according to any one of claims 1 to 3, characterized in that component A and component B are applied to the fibrous material simultaneously or in succession. 5. The method according to any one of claims 1 to 4, characterized in that the carbohydrate derivative on which the formula (I) is based is selected from the group consisting of aldohexoses, aldopentoses, aldofuranoses, aldopyranoses, glycosamines of aldopyranoses, dimeric reducing aldopyranoses and the same formed glycosamines, dimeric reducing aldofuranoses and the glycosamines formed therefrom, trimeric carbohydrates, glycuronic acids, aldonic acids or the lactones formed therefrom. 6. The method according to claim 5, characterized in that the carbohydrate is selected from the group consisting of allose, old rose, galactose, glucose, gulose, idose, mannose, talose, glucosamine, galactosamine, mannosamine, maltose, cellobiose, gentiobiose, lactose, Lactosamine, melezitose, panose, erythrose, threose, ribose, arabinose, xylose, lyxose, glucuronic acid and gluconic acid, gluconic acid-δ-lactone, D-erythronic acid-γ-lactone, D-ribonic acid-γ-lactone, D-xylonic acid-γ- Lactone, D-gulonic acid-γ-lactone, L-gulonic acid-γ-lactone, L-mannonic acid-γ-lactone,, D-glucoheptanoic acid-γ-lactone and, ß-glucooctanoic acid-γ-lactone. 7. The method according to any one of claims 1 to 6, characterized in that in the carbohydrate derivative of the formula (I) a pyranose at position 1 (anomeric center), 2 and / or ö or a furanose at position 1 or 5 is derivatized. 8. The method according to any one of claims 1 to 4, characterized in that a compound according to the following formula (II) or a hydrohalide derived therefrom is used as the carbohydrate derivative

9. The method according to any one of claims 1 to 4, characterized in that N, N ^' -Di-gluconoyl-cystine dimethyl ester is used as the carbohydrate derivative. 10. The method according to any one of claims 1 to 4, characterized in that N, N'-di-gluconoyl-cystamide is used as the carbohydrate derivative. 11. The method according to any one of claims 1 to 10, characterized in that the carbohydrate derivative (component A) and / or the enzyme (component B) are applied to the fibrous material together or in succession in a carrier. 12. The method according to claim 11, characterized in that the carrier is liquid, pasty or gel-like. 13. The method according to any one of claims 11 and 12, characterized in that the carbohydrate derivative (component A) and / or the enzyme (component B) are applied in solution, as a gel or as an emulsion. 14. The method according to any one of claims 1 to 13 for influencing the physical properties of the keratinous material. 15. The method according to claim 14 for influencing gloss, volume, fullness, hold, tactility, moisture, strength and electrostatic properties of the keratinous material and its resistance to the effects of heat, UV and IR radiation. 16. Keratinous, fibrous material obtainable by the process according to one of claims 1 to 15. 17. Compound according to formula (II)

and their hydrohalides. 18. Comprehensive preparation at least one carbohydrate derivative (component A) according to the following formula (I), [Z-Y-R-X] n, (I) where Z is a carbohydrate residue, Y is an amino, thioether, amide, ester or ether group, the group R a linear or branched, saturated or unsaturated, aliphatic or alicyclic hydrocarbon radical having 1 to 12 carbon atoms, which can be substituted by an ester group -COOR ', in which R ^{' is} a C 1 -C ₁₂ -alkyl radical, a single bond, - An arylene, C ₁ -C ₄ -alkylene-arylene or C ₂ -C ₆ -alkenylene-arylene group with 5 to 12 carbon atoms in the arylene radical, which may optionally be substituted with CrC ₆ -alkyl and / or C ₂ - C ₆ alkoxy groups, or - A heteroarylene, CrC ₄ -alkylene-heteroarylene or C ₂ -C ₆ -alkenyl-en-heteroarylene group with 3 to 8 carbon atoms in the heteroarylene radical and one or two heteroatoms (s) selected from N, O and S, which may be substituted with C ₁ -C ₆ -alkyl and / or C ₂ -C ₆ -alkoxy groups, the alkylene, arylene and heteroarylene group in R optionally having at least one oxo, formyl, C ₁ -C ₈ -Acyl- or Cβ-Cio-aryloyl group may be substituted, n = 1 or 2 and X is a thiol group (-SH) for n = 1 and a thioether group (-S-) for n = 2, and / or an enzyme (component B) for which component A has substrate activity. 19. A preparation according to claim 18 comprising a carrier. 20. Preparation according to claim 19, characterized in that the carrier is solid, liquid, gel-like or pasty. 21. Preparation according to one of claims 18 to 20, characterized in that it is present as a solution, gel or emulsion. 22. Preparation according to one of claims 18 to 21 comprising 0.001 to 10 wt .-% of component A, based on the total composition of the composition. 23. Preparation according to one of claims 18 to 22 comprising the enzyme in an amount of 0.1 to 1000 units of enzyme. 24. Preparation according to one of claims 18 to 23, characterized in that it is selected from agents for hair care, detergents and agents for textile and leather care. 25. Preparation according to claim 24, characterized in that the agent is selected from the group consisting of hair shampoos, rinses, sprays, gels, conditioners, finishes, detergents and fabric softeners for textiles and leather. 26. Use of the preparation according to one of claims 18 to 25 for influencing gloss, volume, fullness, hold, tactility, moisture, strength and electrostatic properties of the fibrous material and its resistance to the effects of heat, UV and IR radiation. 27. Kit-of-parts comprising components A and B according to one of the preceding claims, preferably in each case in a preparation according to one of claims 18 to 25, spatially separated from one another. 28. Use of a kit-of-parts according to claim 27 in a method according to one of claims 1 to 15.