DE102005003748A1 - Permanent hair shaping agent useful for carrying out reductive treatment in permanent hair shaping based on hair keratin-reducing compound, comprises cationic cellulose derivative - Google Patents

Abstract

A permanent hair shaping agent (A1) based on at least one hair keratin-reducing compound, comprises a cationic cellulose derivative formed from a cellulose ether with 1000 - 10000 repeating anhydroglucose units, and substituted by anhydroglucose unit. A permanent hair shaping agent (A1) based on at least one hair keratin-reducing compound, comprises a cationic cellulose derivative formed from a cellulose ether with 1000 - 10000 repeating anhydroglucose units, and substituted by 0.0001 - 0.1 moles per anhydroglucose unit of formula R 1R 2R 3R 4N +>[A(z-)] 1 / z (I) and 0.01 - 0.9 moles per anhydroglucose unit of formula R 5R 6R 7R 8N +>[A(z-)] 1 / z (II). R 1, R 2 and R 5 - R 7-CH 3 or -C 2H 5; R 3 and R 8-CH 2-CH(OH)-CH 2- or -CH 2CH 2-; R 4straight or branched 6-24C alkyl; A(z-) : anion selected from chloride, sulfate, nitrate or phosphate; and z : 1 - 3. An independent claim is included for permanently hair shaping involving treating the hair with (A1) before and/or after the hair has been set in a desired form; rinsing the hair with water if necessary after an action period for the permanent shaping; giving an oxidative post-treatment to the hair; rinsing again with water; and set in a hairstyle and finally dried.

Description

The The present invention relates to a thickened means for carrying out the reductive treatment in permanent hair deformation, which contains a specific cationic cellulose derivative, as well as a method for permanent hair deformation using this Agent.

at The permanent hair deformation is usually first with the hair a deforming agent based on a keratin reducing Mercapto compound, which has an opening the disulfide bridges of the Hair keratin causes, treated and then in the desired shape brought. As a deformation agent are usually keratin reducing Mercapto compounds, such as salts or esters of mercaptocarboxylic acids used. Subsequently the hair is rinsed with water and then aftertreated oxidatively with a fixing agent. in this connection The previously split disulfide bridges are re-linked in the new form.

By the chemical action of the hair on this procedure and mechanical processes will the hair quality, especially regarding Grip and combability of the hair, worsens and the hair becomes brittle and rough.

It has already been tried, by adding certain nourishing substances to the shaping agent the hair a smooth, comfortable grip to give as well as the combability to improve the hair. As particularly advantageous here the use of cationic compounds, for example cationic compounds Polymers, proved.

All However, these described hair shaping agents have disadvantages on. To lead this means, for example due to insufficient thickening due to excessive running from the hair, to scalp contacts and thus possible unpleasant skin irritation or due to excessive thickening to an unsatisfactory Deformation of the hair.

Some However, thickeners do not give the shaping agent a cosmetic Appearance being inhomogeneous or a slimy, stringy one or pudding-like consistency.

Long thickening On a polymer basis, moreover, they are not stable for several months Presence of reducing agents and in terms of viscosity (phase separation, Precipitation) and at high pH values or yield by their content reddish on heavy metals discoloration with the corrugated thioglycolate. A special problem also the insufficient dripping resistance, which leads to the corrugating agent reaches the scalp.

Out WO 2005/000903 A1 is the use of certain cationic Cellulosederivaten in means for the care of skin and hair, such as Shampoos and hair products, described - but not in the hair aggressive means, especially those that are strong reducing agents or oxidizing agents.

Even though already numerous cationic cellulose derivatives in pH neutral or weakly acidic hair products have been recommended, are few enough stable, in strong alkaline, reducing hair shaping agents to be used.

It It was therefore the task to provide a means for carrying out the reductive stage to provide for permanent hair deformation during the Treatment time does not expire from the hair, does not drip, the hair still well wetted, as can be present clear gel, a good conditioning the hair allows Easily rinsed out with water is, the agent gives a good cosmetic appearance, stable is good and at the same time one from neck to hair tips uniform deformation result guaranteed.

Surprisingly, it has been found that the stated object is achieved in an outstanding manner, when the permanent hair deformation for the imple out tion of the reductive stage, a Haarverformungsmittel is used which contains a cationic cellulose derivative, which with substituents of For Meln (I) and (II) is substituted.

object The present invention is therefore an agent according to claim 1 and a method for permanent hair deformation according to claim 18th

The preferred embodiments The invention are set forth in the subclaims.

The Advantages of hair styling consist, in addition to the result the viscosity increase simple Application, especially in a significant improvement of grip and combability of permanently deformed hair as well as one from the har-n-set to the hair tips particularly uniform deformation result.

Prefers it is when in the cationic polymer of formula (III) X a Number from 0.1 to 0.6, Y is a number from 0.1 to 0.6, U and V are each a number from 0.001 to 0.06, R is a straight-chain Alkyl radical having 8 to 18 carbon atoms and n is a whole Number is from 1,000 to 6,000.

Especially it is preferred if in the case of the cationic polymer of the formula (III) X = 0.15 to 0.35, Y = 0.15 to 0.35, U and V respectively a number from 0.001 to 0.06, R = a straight-chain alkyl radical from 10 to 16 carbon atoms and n is 2,000 has up to 6,000. More preferably, R = a straight-chain alkyl radical with 12 carbon atoms.

The Hair shaping agent contains the cationic cellulose derivative according to claim 1 advantageous in in an amount of 0.01 to 5% by weight, preferably in one Amount of 0.1 to 2 weight percent, and more preferably in one Amount of 0.1 to 0.5 weight percent.

Cationic cellulose derivatives according to claim 1 are z. B. by the company DOW CHEMICAL / Amerchol under the names Polymer SL ^® -5, Polymer SL ^® -30, Polymer SL ^® -60, Polymer SL ^® -100 distributed, whereby the degree of Hydrophobisie tion (due to the increasing chain length of the substituent R ⁴ or increases with increasing value of the degree of substitution with the substituent (I), with increasing numbers 5, 30, 60 and 100. Their preparation is described, for example, in WO 2005/000903 A1, which are used for the preparation of the cellulose derivatives Cellulose ethers are especially hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and methylcellulose, with hydroxyethylcellulose and hydroxypropylcellulose being preferred.

The The cationic cellulose derivative according to claim 1 has a molecular weight from 10,000 to 4,000,000, preferably from 100,000 to 1,000,000 and preferably a viscosity in 1% aqueous solution from 1,000 to 5,000 mPa · sec at 25 degrees Celsius, more preferably from 1,500 to 3,000 mPa · sec at 25 degrees Celsius: The. viscosity data refer to the measurement with a Haake rotary viscometer type VT 550 at a shear rate of 10.0 per second. It was a double-gap cylinder measuring device type NV or MV used.

It was also surprising found that the cationic cellulose derivatives according to claim 1 as a component of the agent according to the invention, in combination synergistic with another cationic conditioning polymer Way an increase the care properties, in particular the handle and combing hair, both in the dry and in the wet state. In addition, also yet another improved result in terms of uniformity the hair deformation from the approach to the top determined.

The synergistically acting hair conditioning polymers useful in combination with the cationic cellulose derivative of claim 1 may be homopolymers or copolymers wherein the quaternary nitrogen groups are contained either in the polymer chain or preferably as a substituent on one or more of the monomers. The ammonium group-containing monomers may be copolymerized with non-cationic monomers. Suitable cationic monomers are unsaturated, free-radically polymerizable compounds which carry at least one cationic group, in particular ammonium-substituted vinyl monomers such. As trialkylmethacryloxyalkylammonium, Trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary Vinylam moniummonomere with cyclic, cationic nitrogen-containing groups such as pyridinium, imidazolium or quaternary pyrrolidones, z. As alkylvinylimidazolium, alkylvinylpyridinium, or Alyklvinylpyrrolidon salts. The alkyl groups of these monomers are preferably lower alkyl groups such as. B. C ₁ - to C ₇ alkyl groups, more preferably C ₁ - to C ₃ alkyl groups.

Suitable non-cationic comonomers include, for example, acrylamide, methacrylamide, alkyl and dialkylacrylamide, alkyl and dialkylmethacrylamide, alkylacrylate, alkylmethacrylate, vinylcaprolactone, vinylcaprolactam, vinylpyrrolidone, vinylester, e.g. As vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, wherein the alkyl groups of these monomers are preferably C ₁ - to C ₇ alkyl groups, more preferably C ₁ - to C ₃ alkyl groups.

Suitable polymers having quaternary ammonium groups are, for example, the polymers described in the CTFA Cosmetic Ingredient Dictionary under the names POLYQUATERNIUM such. For example, methylvinylimidazolium chloride / vinylpyrrolidone copolymer (POLYQUATERNIUM-16) or quaternized vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (POLYQUATERNIUM-11). Homopolymers and copolymers of dimethyldiallylammonium chloride, such as. B. polydimethyl diallyl ammonium chloride (Polyquaternium-6), sold by the company Ondeo Nalco under the trade name Merquat ^® 100, or the copolymers of acrylamide and dimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-7); quaternized hydroxyethylcellulose (POLYQUATERNIUM-10) or quaternized guar derivatives.

Among the cationic polymers that can be included in the inventive composition, for example vinylpyrrolidone / dimethylaminoethyl copolymer available under the trade names Gafquat ^® 755 N and Gafquat ^® 734 Co., USA is sold by Gaf and of which the Gafquat ^® 734 is particularly preferred suitable. Other cationic polymers are for example sold by the company BASF, Germany, under the trade name LUVIQUAT ^® HM 550 and LUVIQUAT ^® HM 552 displaced copolymers of polyvinyl pyrrolidone and imidazolimine which ^® by the company Calgon / USA under the trade name Merquat Plus 3300 sold terpolymer of dimethyl diallyl ammonium chloride, sodium acrylate and acrylamide by ISP / USA under the trade name Gaffix ^® VC 713 displaced terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam and sold by GAF under the trade name Gafquat ^® HS 100 vinylpyrrolidone / methacrylamidopropyltrimethylammonium copolymer.

suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example cationic derivatives of starch or guar. Also suitable are chitosan and chitosan derivatives.

Cationic polysaccharides have the general formula GOBN ⁺ R ^a R ^b R ^c X ^- (IV) G is an anhydroglucose residue, for example starch or cellulose anhydroglucose;
B is a divalent linking group, for example, alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene; R ^a , R ^b and R ^c are each independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having 1 to 18 carbon atoms, wherein the total number of carbon atoms in R ^a , R ^b and R ^c preferably not more than 20 is; X ^(-) is a common anion, preferably chloride, bromide or sulfate.

A suitable cationic cellulose of the formula (IV) is sold under the name of Polymer JR ^® by the company Amerchol, and has the INCI designation Polyquaternium-10 degrees. A further cationic cellulose has the INCI designation Polyquaternium-24 and is sold under the trade name Polymer LM ^® -200 from Amerchol. A suitable cationic guar derivative is sold under the trade name Jaguar ^® R and has the INCI name, guar hydroxypropyltrimonium chloride.

Further suitable cationic polymers are chitosan, chitosan salts and Chitosan derivatives. The chitosans are complete or partially deacetylated chitin. For the production of Chitosan goes preferably from that in the shell remnants of crustaceans contained chitin, which is cheaper and more natural Raw material in big Quantities available stands. The molecular weight of chitosan can be distributed over a broad spectrum be, for example, from 20,000 to about 5,000,000 g / mol. Suitable is, for example, a low molecular weight chitosan having a molecular weight from 30,000 to 70,000 g / mol. Preferably, the molecular weight is however over 100,000 g / mol, more preferably from 200,000 to 700,000 g / mol. The degree of deacetylation is preferably 10 to 99%, more preferably 60 to 99%.

A suitable chitosan is sold for example by Kyowa Oil & Fat, Japan, under the trade name Flonac ^®. It has a molecular weight of 300,000 to 700,000 g / mol and is deacetylated to 70 to 80%. A preferred chitosan salt is chitosonium pyrrolidone carboxylate which, for example, is sold under the name Kytamer PC by Amerchol, USA. The contained chitosan has a molecular weight of about 200,000 to 300,000 g / mol and is deacetylated to 70 to 85%. Suitable chitosan derivatives are quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethyl or hydroxybutylchitosan.

The Chitosans or chitosan derivatives are preferably in neutralized or partially neutralized form. The degree of neutralization for the Chitosan or the chitosan derivative is preferably at least 50%, more preferably between 70 and 100%, based on the number the free base groups. As a neutralizing agent can in principle all cosmetically acceptable inorganic or organic acids used be like Formic acid, Malic acid, Succinic acid, Tartaric acid, Citric acid, malonic, oxalic acid and pyrrolidonecarboxylic acid; of which the citric acid is preferred.

Further suitable cationic hair care compounds that are used in the inventive deformation means may be included are cationically modified protein derivatives or cationically modified Protein hydrolysates and are known, for example, under the INCI names Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein or Hydroxypropyltrimoni to Hydrolyzed Wheat; hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyltrimonium Hydrolyzed Vegetable Protein.

suitable cationically derivatized protein hydrolysates are substance mixtures, For example, by the reaction of alkaline, acidic or enzymatic hydrolyzed proteins with glycidyl trialkylammonium salts or 3-halo-2-hydroxypropyl trialkyl ammonium salts can be obtained. Proteins that serve as starting materials for the protein hydrolysates, can be both of plant and animal origin. Usual starting materials are, for example, keratin, collagen, elastin, soy protein, rice protein, Milk protein, wheat protein, silk protein or almond protein. By the hydrolysis produces mixtures of substances with molecular weights in the range from about 100 to about 50,000. usual average molecular weights are in the range of about 500 to about 1000. Advantageously, the cationically derivatized protein hydrolysates contain one or two long C8 to C22 alkyl chains and correspondingly two or one short C1 to C4 alkyl chains. Links, which contain a long alkyl chain are preferred.

suitable Finally, cationic polymers are also cation-active silicone compounds. These are substituted with cationic or cationizable groups. Suitable cationic silicone compounds are either at least an amino group or at least one ammonium group. suitable Silicone polymers with amino groups are under the INCI name AMODIMETHICONE known. These are polydimethylsiloxanes with aminoalkyl groups. This is particularly suitable by the company Dow Chemical under the trade name DC2-8556 (CTFA: AMODIMETHICONE) and that of the subsidiary Osi of the company General Electric under the trade name Silsoft A-858 (CTFA: DEA PG-PROPYL PEG / PPG-18/21 DIMETHICONE) sold polymer.

It is particularly preferable that the synergistically effective cationic polymer contained in the permanent shaping agent of the present invention in addition to the cationic cellulose derivative of claim 1 is selected from: diallyldimethylammonium chloride / hydroxyethylcellulose copolymers (CTFA: POLYQUATERNIUM-4), beta-methacryloxyethyltrimethylammonium methosulfate / acrylamide copolymers (CTFA : POLYQUATERNIUM-5), polydiallyldimethylammonium chloride (CTFA: POLYQUATERNIUM-6), e.g. As sold by the company Ondeo Nalco under the trade name Merquat ^® 100, copolymers of acrylamide and dimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-7), quaternized vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (POLYQUATERNIUM-11), polydimethylaminoethyl methacrylate (75% with dimethyl sulfate or to 100% quaternized with methyl chloride or methyl bromide), beta-methacryloxyethyltrimethylammonium methosulfate homopolymer (CTFA: POLYQUATERNIUM-14), beta-methacrylyloxyethyltrimethylammonium chloride / methacrylamide copolymers (CTFA: POLYQUATERNIUM-15), methylvinylimidazolium chloride / vinylpyrrolidone copolymer (CTFA: POLYQUATERNIUM-16); N-vinylpyrrolidone / Methacrylamidopropyltrimethylammoniumchlorid copolymers, acrylic acid polymers such. As the marketed by the company Röhm GmbH under the trade name PLEX 3074 L polymer (CTFA: POLYQUATERNIUM-35) and cationic guar derivatives and cationic chitosan derivatives.

As a keratin-reducing active ingredient in the shaping agent sulfites or mercapto compounds such as in particular thioglycolic acid, glycerol esters of thioglycolic acid, thioglycolic acid amides, thioglycerol, thiolactic acid, 3-mercaptopropionic acid, cysteine, cysteine derivatives such as. As cysteine-2-hydroxyethyl, cysteamine, homocysteine, alkyl or acylcysteine, mercaptoacetamides, 2-Mercaptopropionsäureamide or the salts or derivatives of these compounds, in particular ammonium thioglycolate. The keratin-reducing agent is contained in the ready-to-use permanent hair-styling agent in an amount of 1 to 25% by weight, preferably 5 to 15% by weight.

Advantageous contains the permanent shaping agent in addition the disulfide of a hair keratin reducing mercaptan, in particular Dithioglykolat. The preferred use amount for the disulfide is 1 to 20 Wt.%, Preferably 2 to 10 wt.%, Where a ratio between hair keratin reducing compound and the disulfide from 2: 1 to 1: 2, in particular 2: 1 to 1: 1, is preferred.

Of course you can the ready-to-use permanent deformation agent all for such Medium usual and known additives, for. B. thickeners, such as fatty acids, Hydroxyethylcellulose, starch, Vaseline, paraffin oils; Wetting agents or emulsifiers from the classes of cationic, amphoteric or nonionic surface active Substances, such as quaternary Ammonium salts, e.g. Cetyltrimethylammonium chloride, N-alkylbetaines and N-alkylamidobetaines, N-alkylsulfobetaines, N-alkylaminopropionates, alkyldimethylcarboxymethylammonium salts with 12 to 18 carbon atoms and fatty acid alkylamidobetaines, for example Fettsäureamidopropyldimethylaminoessigsäurebetain, ethoxylated alkylphenols, fatty acid alkanolamides or ethoxylated fatty acid esters; furthermore opacifiers, such as As polyethylene glycol esters, alcohols, such as ethanol, Propanol, isopropanol, polyols such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol and glycerin; Sugar such as B. D-glucose, solubilizers such. B. dipropylene glycol monomethyl ether, hydrogenated and ethoxylated castor oil, ethoxylated fatty alcohols, Stabilizers, alkalizing agents, e.g. As ammonia, mono- or Diethanolamine, buffer substances, eg. For example, ammonium bicarbonate, Perfume oils, dyes as well as hair conditioning and hair care ingredients, such as. Lanolin derivatives, urea, cholesterol, pantothenic acid and betaine, contain.

The mentioned Ingredients are used in the permanent deformation agent the for such purposes usual Used quantities, z. As the wetting agents and emulsifiers in concentrations of a total of 0.2 to 30 wt.%, the alcohols in an amount of a total of 0.1 to 20 wt.%, The opacifiers, perfume oils and dyes in an amount of 0.01 to 1 wt.%, The buffer substances in a total amount of 0.1 to 10% by weight, sugar, solubilizer, Stabilizers, as well as hair conditioning and hair care ingredients in an amount of 0.1 to 5 wt.% each, while the thickeners and solver in a total amount of 0.5 to 20 wt.% Contained in this agent could be.

Farther can in this means to increase the effect so-called swelling and penetration substances, such as z. Dipropylene glycol monomethyl ether, 2-pyrrolidone or imidazolidin-2-one, be contained in an amount of 1 to 30 wt.%.

The inventive agent has expediently a viscosity from 1.5 to 5,000 mPa · s at 25 degrees Celsius; wherein a viscosity of 3 to 3,000 mPa · s at 25 degrees Celsius is preferred.

The pH of the deforming agent is preferably 7 to 10, wherein the adjustment is preferably carried out with ammonia, monoethanolamine, ammonium carbonate or ammonium bicarbonate. When the deforming agent is acidic (for example, pH = 6.5 to 6.9), esters of mercaptocarboxylic acids such as monothioglycolic acid glycol ester or glycerol ester, but preferably mercaptoacetamide or 2-mercaptopropionic acid amide, in a concentration of 2 to 14% by weight; or the salts of sulfurous acid, for example, sodium, ammonium or monoethanolammonium sulfite, in a concentration of 3 to 8 weight percent (calculated as SO ₂ ) used.

One Another object of the present invention is a method for permanent hair deformation, in which one before the hair and / or after you put it in the desired Form brings with a hair keratin reducing deformation agent treated, after a for the permanent deformation of the hair sufficient exposure time if necessary rinse the hair with water, then the hair with a Oxidative post-treated fixative, rinsed again with water, for Hairstyle lays and finally dries, which is characterized in that as a deformation agent used the above-described inventive deformation agent becomes.

In the method according to the invention, the hair is washed, toweled with a towel, in a split individual strands and wound on winder. The diameter of the winder is hereby, depending on whether a Dauerwellung or a hair detangling is desired, either 5 to 13 millimeters or about 15 to 35 millimeters. On the hair before and / or after winding on winder sufficient for the permanent hair deformation amount of the deformation agent according to the invention is applied. The total amount of the deforming agent required for permanent hair deformation is generally about 80 to 120 grams.

To one for the permanent deformation of the hair sufficient exposure time, which depending on hair condition, the deformation efficiency of Deforming agent and depending from the application temperature 5 to 30 minutes (10 to 30 minutes without heat or 5 to 20 minutes with heat) is, the hair is rinsed with water and then oxidatively treated ("fixed"). The fixative is, depending on the hair, preferably in an amount of 80 to 100 grams, used.

When Fixative for The hair in wound or unwound state can be any any, for one Such treatment used suitable known per se fixative become. examples for oxidants usable in such fixatives are potassium and sodium bromate, sodium perborate, urea and hydrogen peroxide. The concentration of the oxidizing agent is dependent from the application time (usually 5 to 15 minutes) and the application temperature differently. Normally the oxidizing agent is present ready-to-use aqueous Fixing agent in a concentration of 0.5 to 10 wt.% Before. The Fixative can of course other substances, such as. As wetting agents, care agents such as betaine, weak acids, buffer substances or peroxide stabilizers, and in the form of an aqueous Solution, an emulsion and in thickened form on an aqueous basis, in particular as a cream, gel or paste. These usual additives can be used in particular Amount of 0.1 to 10 wt.% To be contained in the fixing agent.

Then be the winder removed. If necessary, the settled Hair can now be post-treated oxidatively. Then the hair becomes rinsed with water, optionally placed to the water wave and finally dried.

The thus treated hair has a uniform and durable deformation and is excellently conditioned.

The The following examples serve to explain the subject of the present invention.

Example 1 Tear-resistant mild alkaline perming agent for normal hair 18.20 g Ammonium thioglycolate (70% aqueous solution) 2,00 g Ammonia (25% aqueous solution) 4.00 g ammonium 0.15 g Cellulose derivative according to formula (III) with a viscosity of 2,112 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -60) 0.20 g Polydimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-6) 0.20 g Vinyl pyrrolidone / dimethylaminoethyl methacrylate methosulfate copolymer (CTFA: POLYQUATERNIUM-11) 1.00 g 1,3-butanediol 1.50 g 1,2-propylene glycol 2,00 g dipropylene glycol 3.50 g urea 1.00 g hydrogenated ricinustriglyceride polyglycol ether (CTFA: PEG-40 HYDROGENATED CASTOR OIL) 1.00 g Oxyethylated coconut fatty alcohol ethoxylated with 8 moles of ethylene oxide (CTFA: COCETH-8) 0.50 g perfume oil ad 100.00 g water

After winding the hair on permanent wave winder, the above permanent wave agent of pH = 8.4 and a viscosity of 8.5 mPa · sec at 25 degrees Celsius is evenly applied to the winder. Then there is an exposure time of 10 minutes using an infrared radiator hood at a temperature of 40 ° C. The hair is rinsed with water. Then, the winder 80g of a following fixing agent is applied. fixer 4.00 g Hydrogen peroxide, 50% 0.10 g salicylic acid 0.20 g disodium 0.15 g o-phosphoric acid 1.00 g ethoxylated with 35 moles of ethylene oxide castor oil 0.10 g Vinylpyrrolidone / styrene copolymer 0.10 g perfume oil ad 100 g water

After an exposure time of 8 minutes, the fixative is rinsed with water and the hair unwound. The hair shows a neat appearance, a pleasant grip and good wet combability and a uniform wave pattern. Example 2 Tear-resistant mild alkaline permanent waving agent for dyed hair 12.50 g Ammonium thioglycolate (70% aqueous solution) 2,00 g Diammoniumdithioglykolat 0.80 g Ammonia (25% aqueous solution) 4.00 g ammonium 0.15 g Cellulose derivative of the formula (III) with a viscosity of 2,112 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -60) 0.80 g Polydimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-6) 0.20 g amino-functional silicone polymer (CTFA: METHOXY PEG / PPG-7/3 AMINOPROPYL DIMETHICONE) 0.10 g hydroxyethyl 0.30 g Styrene / vinylpyrrolidone copolymer (CTFA: STYRENE / VP COPOLYMER) 1.50 g 1,2-propylene glycol 2,00 g dipropylene glycol 2,00 g urea 1.00 g hydrogenated ricinustriglyceride polyglycol ether (CTFA: PEG-40 HYDROGENATED CASTOR OIL) 1.00 g Oxyethylated coconut fatty alcohol (CTFA: CoCETH-8) with 8 moles of ethylene oxide 0.50 g perfume oil ad 100.00 g Water (pH = 8,2)

After winding the hair on permanent wave winder, the above permanent wave agent of pH = 8.2 and a viscosity of 11 mPa · sec is applied evenly to the winder at 25 degrees Celsius. Then there is an exposure time of 20 minutes at room temperature. The hair is rinsed with water. Then are applied to the winder 80g of the fixing agent of Example 1: After a contact time of 10 minutes, the fixing agent is rinsed with water and the hair unwound. The hair shows a neat appearance, a pleasant grip and good wet combability and a uniform wave pattern. Example 3 Tear-resistant mild alkaline perming agent for hair that is difficult to curl 26.50 g Monoethanolamine thioglycolate (67% aqueous solution) 3.80 g Monoethanolamine 0.10 g Polymer of formula (III) with a viscosity of 1,710 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -5) 0.30 g Quaternized Vinyl Pyrrolidone / Dimethylaminoethyl Methacrylate Copolymer (POLYQUATERNIUM-11) 0.02 g hydroxyethyl 1.00 g 1,3-butanediol 1.50 g 1,2-propylene glycol 2,00 g dipropylene glycol 3.50 g urea 1.50 g oxyethylated with 10 moles of ethylene oxide oleyl alcohol (CTFA: OLETH-10) 0.50 g perfume oil ad 100.00 g Water (pH = 8.9)

The permanent wave agent has a viscosity of 5.5 mPa · sec at 25 degrees Celsius. The application is made as in Example 2. The hair shows a neat appearance, a pleasant grip and good wet combability and a uniform wave pattern. Example 4 2-Component Drip-resistant Perming Agent Component 1 1.50 g ammonium 2.20 g Ammonia (25% aqueous solution) 0.10 g Polymer of formula (III) with a viscosity of 1,895 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -30) 0.10 g Polymer of formula (III) with a viscosity of 2,205 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -100) 0.40 g Methylvinylimidazolium chloride / vinylpyrrolidone copolymer (CTFA: POLYQUATERNIUM-16) 0.30 g cetyltrimethylammonium 1.50 g 1,2-propylene glycol 3.00 g urea 1.80 g Oleyl alcohol ethoxylated with 20 moles of ethylene oxide (CTFA: OLETH-20) 0.40 g perfume oil ad 100.00 g water Component 2 80.00 g Ammonium thioglycolate (70% aqueous solution) 20.00 g Ammonium thiolactate (70% aqueous solution)

Before use, 60 g of component 1 are mixed with 15 g of component 2. The pH of the ready-to-use hair-styling agent obtained is 7.3. Apply 75 g of the ready-to-use agent to hair previously wound on a permanent wave winder of 8 mm diameter and let it act for 20 minutes at room temperature. The hair is then rinsed with water. Then are applied to the winder 80g of the fixing agent of Example 1. After a contact time of 10 minutes, the fixative is rinsed with water and the hair unwound. The hair shows a neat appearance, a pleasant grip and good wet combability and a uniform wave pattern. Example 5 Gel-type permanent waving agent for batch refreshment 18.20 g Ammonium thioglycolate (70% aqueous solution) 2.20 g Ammonia (25% aqueous solution) 3.50 g ammonium 0.30 g Polymer of formula (III) with a viscosity of 2,112 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -60) 0.20 g Polydimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-6) 0.80 g hydroxyethyl 0.50 g 1,3-butanediol 2,00 g 1,2-propylene glycol 2,00 g dipropylene glycol 3.50 g urea 1.50 g Polyethylene glycol ricinus oil (35EO) (CTFA: PEG-35 GASTOR OIL) 1.00 g hydrogenated ricinustriglyceride polyglycol ether (40EO) (CTFA: PEG-40 HYDROGENATED CASTOR OIL TRIISOSTEARATE) 0.50 g perfume oil ad 100.00 g Water (pH = 8,6)

After winding the hair on permanent wave winder, the above gel permanent wax of pH = 8.6 and a viscosity of 2700 mPa · sec at 25 degrees Celsius is applied with a brush in each case on the neck hair. Then there is an exposure time of 10 minutes at room temperature. The hair is rinsed with water. Then are applied to the winder 60g of the fixing agent of Example 1. After a contact time of 10 minutes, the fixative is rinsed with water and the hair unwound. The hair shows a good approach wave, an excellent grip and a good combability. Example 6 2-phase permanent waving agent to compensate for large structural differences in hair Phase 1 12.50 g Ammonium thioglycolate (70% aqueous solution) 0.80 g Ammonia (25% aqueous solution) 4.00 g ammonium 0.10 g Polymer of formula (III) with a viscosity of 2,112 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -60) 0.10 g Polymer of formula (III) with a viscosity of 2,205 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -100) 0.80 g Amino silicone DC2-8566 from Dow Corning (CTFA: AMODIMETHICONE) 0.30 g Styrene / vinylpyrrolidone copolymer (CTFA: STYRENE / VP COPOLYMER) 1.50 g 1,2-propylene glycol 2,00 g urea 1.00 g Coconut fatty alcohol ethoxylated with 8 moles of ethylene oxide (CTFA: COCETH-8) 1.00 g hydrogenated ricinustriglyceride polyglycol ether (40EO) (CTFA: PEG-40 HYDROGENATED CASTOR OIL TRIISOSTEARATE) 0.50 g perfume oil ad 100.00 g Water (pH = 8,2) Phase 2 18.20 g Ammonium thioglycolate (70% aqueous solution) 2.20 g Ammonia (25% aqueous solution) 3.50 g ammonium 0.40 g Polymer of formula (III) with a viscosity of 2,112 mPa · sec at 25 ° C in 1% aqueous solution (Amerchol Polymer SL ^® -60) 0.20 g Polydimethyldiallylammonium chloride (CTFA: POLYQUATERNIUM-6) 0.80 g hydroxyethyl 0.50 g 1,3-butanediol 2,00 g 1,2-propylene glycol 2,00 g dipropylene glycol 3.50 g urea 1.50 g Polyethylene glycol ricinus oil (35EO) (CTFA: PEG-35 CASTOR OIL) 1.00 g hydrogenated ricinustriglyceride polyglycol ether (40EO) (CTFA: PEG-40 HYDROGENATED CASTOR OIL TRIISOSTEARATE) 0.50 g perfume oil ad 100.00 g Water (pH = 8,6)

To the winding of the hair on permanent wave winder, is the first liquid Permanent wave phase 1 of pH = 8.2 and a viscosity of 7 mPa · sec applied to the reels at 25 degrees Celsius. Immediately afterwards On each roll is the above gel permeable from pH = 8.6 and a viscosity of 2,900 mPa · sec at 25 degrees Celsius with a brush on the approach hair applied. Then there is an exposure time of 10 minutes at room temperature. After that, the hair is rinsed with water. thereupon are applied to the winder 60g of the fixing agent of Example 1. After a contact time of 10 minutes, the fixative rinsed with water and the hair unwound. The hair shows a uniform wave from the hairline to the hair tip, an excellent grip and a very good combability.

All in the present application contained percentages - so far not stated otherwise - weight percent represents.

All viscosity data refer to the measurement with a Haake rotary viscometer Type VT 550 at a shear rate of 10.0 per second. It was a double-gap cylinder measuring device type NV or MV used.

Claims (18)

Composition for carrying out the reductive stage in permanent hair shaping, based on at least one hair keratin-reducing compound, characterized in that it contains a cationic cellulose derivative formed from a cellulose ether having from 1,000 to 10,000 repeating anhydroglucose units comprising (a) per anhydroglucose unit 0.0001 to 0.1 moles of a substituent of the formula R ¹ R ² R ³ R ⁴ N ⁺ (A ^z- ) _{1 / z} (I) R ¹ and R ^{2 are} independently -CH ₃ or -C ₂ H ₅ , R ^{3 is} -CH ₂ -CH (OH) -CH ₂ - or -CH ₂ CH ₂ -, R ^{4 is} a straight chain or branched alkyl having 6 to 24 carbon atoms, A ^{z is} an anion selected from chloride, sulfate, nitrate or phosphate, and z is 1, 2 or 3, and (b) per anhydroglucose unit at 0.01 to 0.9 moles of a substituent of the formula R ⁵ R ⁶ R ⁷ R ⁸ N ⁺ (A ^z- ) _{1 / z} (II) is substituted, wherein R ⁵ , R ⁶ and R ^{7 are} independently -CH ₃ or -C ₂ H ₅ , R ^{8 is} -CH ₂ -CH (OH) -CH ₂ - or -CH ₂ CH ₂ -, A ^z- Anion selected from chloride, sulfate, nitrate or phosphate, and z is 1, 2 or 3. Composition according to claim 1, characterized in that in formula (I) R ¹ and R ^{2 have} the meaning -CH ₃ and R ^{3 has} the meaning -CH ₂ -CH (OH) -CH ₂ - has. Composition according to claim 1 or 2, characterized in that in the formula (I) R ^{4 has} the meaning of straight-chain or branched alkyl radical having 10 to 16 carbon atoms. Agent according to one of claims 1 to 3, characterized in that ⁷ is -CH have in the formula (II) R ^5, R ⁶ and R. ₃ Agent according to one of claims 1 to 4, characterized in that in the formula (II) R ^{8 has} the meaning -CH ₂ -CH (OH) -CH ₂ - has. Agent according to one of claims 1 to 5, characterized in that it is a cationic cellulose derivative of the general formula (III),

wherein, X is a number from 0.05 to 0.8, Y is a number from 0.05 to 0.8, U is a number from 0.0005 to 0.05, V is a number from 0.0005 to 0 , 05, R is a straight-chain or branched alkyl radical having 6 to 18 carbon atoms and n is an integer from 1,000 to 8,000 contains. Composition according to claim 6, characterized in that in the formula (III) R = C ₁₂ H ₂₅ . Agent according to one of claims 1 to 7, characterized that the cationic cellulose derivative in 1% by weight aqueous solution a viscosity from 1,500 to 3,000 mPa · sec at 25 degrees Celsius, measured with a Haake rotary viscometer Type VT 550 at a shear rate of 10.0 per second, having. Agent according to one of claims 1 to 8, characterized that the cationic cellulose derivative in an amount of 0.1 to 5 weight percent is included. Agent according to one of claims 1 to 9, characterized in that it additionally contains at least one cationic polymer selected from polydimethylaminoethyl methacrylate (75% dimethyl sulfate or 100% quaternised with methyl chloride or methyl bromide), polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / hydroxyethylcellulose copolymers , beta-methacryloxyethyltrimethyl Ammonium Methosulfate Homopolymer, Beta-Methacryloxyethyltrimethylammonium Methosulfate / Acrylamide Copolymers, Beta-Methacrylyloxyetliyltrimethylammonium Chloride / Methacrylamide Copolymers, Copolymers of Acrylamide and Dimethyldiallylammonium Chloride, Vinylpyrrolidone / Dimethylaminoethyl Methacrylate Copolymer, Beta-Methacryloxyethyltrimethylammonium Methosulfate / Vinylpyrrolidone Copolymers, Methylvinylimidazolium Chloride / Vinylpyrrolidone Copolymer, Diallyldimethylammonium Chloride / Acrylamide Copolymers, N-vinylpyrrolidone / methacrylamidopropyldimethylammonium chloride copolymers, cationic chitosan derivatives, cationic cellulose derivatives other than cationic cellulose derivatives of claim 1, and cationic guar derivatives. Agent according to one of claims 1 to 10, characterized the total amount of cationic polymers is from 0.2 to 5% by weight is. Agent according to one of claims 1 to 11, characterized that the hair keratin reducing compound is selected from thioglycolic acid, Cysteine or thiolactic acid or their salt. Agent according to one of claims 1 to 12, characterized that the hair keratin reducing compound in the permanent shaping agent contained in an amount of 2 to 15% by weight. Agent according to one of claims 1 to 13, characterized that the permanent shaping agent is the disulfide of a hair keratin reducing Contains connection. Agent according to claim 14, characterized the disulphide of the hair keratin reducing compound is dithioglycolate is. Agent according to one of claims 14 or 15, characterized that the disulfide of the hair keratin reducing compound in one Amount of 2 to 20 wt.% Is included. Agent according to one of claims 14 to 16, characterized that the ratio of the hair keratin reducing compound to the disulphide of the hair keratin reducing Compound 2: 1 to 1: 1. Method for permanent hair deformation, in which to get the hair before and / or after you have it in the shape you want treated with a hair keratin reducing agent, after a for the permanent deformation of the hair sufficient exposure time, if necessary rinse the hair with water, then the hair oxidatively after-treatment, rinsing again with water, applying to hairstyle and finally drying, characterized in that as a hair keratin reducing deformation agent an agent according to any one of claims 1 to 17 used.