WO2001010395A1

WO2001010395A1 - Use of synthetic polymers

Info

Publication number: WO2001010395A1
Application number: PCT/EP2000/007165
Authority: WO
Inventors: Gabriele Munk; Thomas Schröder; Marcus Krueger; Elisabeth Poppe
Original assignee: Hans Schwarzkopf Gmbh & Co. Kg
Priority date: 1999-08-05
Filing date: 2000-07-26
Publication date: 2001-02-15
Also published as: AU6566500A; DE19936910A1; EP1200045A1

Abstract

The washability of dyed fibers, especially keratin fibers, is noticeably increased by the use of synthetic polymers whose 0.75 % preparation has a viscosity of at least 10,000 mPas in water at 20 °C.

Description

USE OF SYNTHETIC POLYMERS

The invention relates to the use of synthetic polymers to improve the wash fastness of dyeings of keratin fibers, corresponding preparations and methods for dyeing 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. Apart from the bleaching agents, which bring about an oxidative brightening of the hair by breaking down the natural hair dyes, there are essentially three types of hair dye in the area of hair coloring:

So-called oxidation colorants are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation colorants are characterized by excellent, long-lasting coloring results. For natural-looking dyeings, however, a mixture of a large number of oxidation dye precursors usually has to be used; in many cases direct dyes are still used for shading. If the dyes formed or used directly in the course of the color formation have distinctly different fastness properties (e.g. UV stability, fastness to perspiration, fastness to washing, etc.), a recognizable and therefore undesirable color shift can occur over time. This phenomenon increases when the hairstyle has hair or hair zones with different degrees of damage. One example of this is long hair, in which the hair tips, which have been exposed to all possible environmental influences for a long time, are generally significantly more damaged than the relatively freshly regrown hair zones.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally significantly more sensitive to shampooing than the oxidative dyeings, so that a much undesired shift in nuances or even a visible "discoloration" occurs much more quickly.

After all, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally analogous dyes in the hair as part of oxidative processes. Such a process with 5,6-dihydroxyindoline as a dye precursor was described in EP-B 1-530 229. When using agents with 5,6-dihydroxyindoline, in particular several times, it is possible to reproduce the natural hair color for people with gray hair. The coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used. For people with originally medium blonde to brown hair, indoline can be used as the sole dye precursor. For use in people with originally red and in particular dark to black hair color, however, satisfactory results can often only be achieved by using additional dye components, in particular special oxidation dye precursors. Problems with the authenticity of the dyeings can also occur here. Efforts have therefore been made to improve the authenticity of dyeings of keratin fibers. One development direction is the optimization of the dyes themselves or the synthesis of new, modified dye molecules. Another direction of development is the search for additives for the colorants in order to increase the authenticity of the dyeings. A known solution to the problem is to add UV filters to the colorant. These filter substances are applied to the hair together with the dye during the dyeing process, which in many cases results in a significant increase in the stability of the dyeing against the action of daylight or artificial light.

It has now surprisingly been found that the washfastness of dyeings, in particular keratin fibers, can be significantly increased by using certain synthetic polymers. Under washfastness in the sense of the invention, the maintenance of the original coloring with regard to nuance and / or intensity is to be understood when the keratinic fiber is exposed to the repeated influence of aqueous agents, in particular surfactants, such as shampoos.

A first object of the present invention is therefore the use of synthetic polymers whose 0.75% preparation in water at 20 ° C has a viscosity of at least 10,000 mPas to improve the wash fastness of dyeings of fibers, in particular keratin fibers.

The polymers used according to the invention improve the fastness to washing of dyeings on artificial fibers such as polyesters and natural fibers such as cotton and in particular keratin fibers.

According to the invention, keratin fibers are understood to mean furs, wool, feathers and in particular human hair.

Polymers whose 0.75% preparation in water (ie a mixture of 0.75 g of polymers and 90.25 g of water) can be used according to the invention at a temperature of 20 ° C has a viscosity of at least 10,000 mPas. The viscosity is determined using a Brookfield RVT viscometer using spindle 5 at 20 revolutions per minute. These polymers are referred to as color-preserving polymers in the further course.

According to a first preferred embodiment, the color-retaining polymer is an anionic polymer which has carboxylate and / or sulfonate groups.

Examples of anionic monomers from which the color-retaining polymers can consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer have proven to be very particularly effective, the sulfonic acid group being able to be present in whole or in part as the sodium, potassium, ammonium, mono- or triethanolammonium salt ,

Within this first embodiment, it may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone, vinyl ether and vinyl ester.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred Networking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid is obtainable for example under the name Rheothik ^® 11-80 commercially.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be crosslinked, with polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene bisacrylamide preferably being used as crosslinking agents. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C ₁₃ -C, _4- isoparaffin) and a nonionic emulsifier (Laureth-7), has proven to be particularly advantageous in the context of the teaching according to the invention.

Also, as a compound with isohexadecane and sold under the name Simulgel ^® 600 Polysorbate-80 sodium acryloyldimethyltaurate copolymers have proven effective as in the present invention particularly.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-preserving polymers. A cross-linked with 1,9-decadiene maleic acid-methyl vinyl ether copolymer is available under the name Stabileze® ^® QM. According to a second embodiment, the color-retaining polymer is a cationic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C _M hydrocarbon group to a main polymer chain composed of acrylic acid, methacrylic acid or their derivatives have proven to be particularly suitable. Homopolymers of the general formula (I),

R ¹

I

- [CH, -C-] _n X- (I)

I

CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ⁴ are selected independently of one another from C _M alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n a natural number and X ^"is a physiologically compatible organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (I) and nonionic monomer units are particularly preferred cationic color-retaining polymers. Within the scope of these polymers, those preferred according to the invention are for which at least one of the following conditions applies:

R ¹ represents a methyl group

- R ² , R ³ and R ⁴ represent methyl groups

- m has the value 2,

Suitable physiologically compatible counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, in particular chloride, are preferred. A particularly suitable homopolymer is the, if desired crosslinked, poly (memacryloyloxyethyltrimethylaj3imomumchlorid) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, monnitol, sorbitol or sucrose. Methylene bisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (approx. 50% polymer content, further components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth- 6)) and Salcare ^® SC 96 (approx. 50% polymer content, further components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol Dicaprylate / Dicaprate) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.

Copolymers with monomer units according to formula (I) preferably contain acrylamide, methacrylamide, C-alkyl-alkyl ester and C-alkyl-methacrylate as non-ionic monomer units. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloyloxyemyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

It is also possible according to the invention that the preparations contain several color-preserving polymers. In this case it is preferred to use polymers of the same ionogenicity. The color-retaining polymers are preferably present in the agents used according to the invention in amounts of 0.05 to 5% by weight, based on the total agent. Amounts from 0.1 to 3, in particular from 0.2 to 1% by weight are particularly preferred.

It has furthermore been found that the color-preserving action of the abovementioned polymers can surprisingly be increased significantly if these polymers are used in combination with a protein hydrolyzate or a derivative of a protein hydrolyzate.

Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).

According to the invention, protein hydrolyzates of both vegetable and animal origin can be used.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Henkel), Promois ^® (Interorgana), Collapuron ^® (Henkel), Nutrilan ^® (Grünau), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda) sold.

According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, pea, potato and wheat protein hydrolyzates. Such products are available, for example, under the trademarks Gluadin ^® (Henkel), DiaMin ^® (Diamalt), Lexein ^® (Inolex) and Crotein ^® (Croda).

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally 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. Such products are, for example, under the names Lamepon ^® (Henkel), Lexein ^® (Inolex), Crolastin ^® (Croda), Crotein ^® (Croda), Lamequat ^® and Croquat ^® .

The protein hydrolyzates or their derivatives are preferably contained in the agents used according to the invention in amounts of 0.1 to 5% by weight, based on the total agent. Amounts of 0.1 to 2% by weight are particularly preferred.

The combination of the color-retaining polymers with cationic surfactants has also proven to be advantageous.

Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines are preferred according to the invention. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammomum 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.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as 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 inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

Alternatively or in combination with the cationic surfactants, cationic polymers can also be used according to the invention.

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 and thus cationically at certain pH values. However, among the cationic polymers, the permanently cationic polymers are preferred. According to the invention, permanently cationic "are those polymers which have a cationic group irrespective of the pH of the agent. 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, polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone) , Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80), cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® , Polymeric dimethyl diallyl ammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammomum chloride-acrylamide copolymer) are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially VinylpyπOlidon-vinylimidazoliummethochloride copolymers, such as those offered under the names Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM 552nd quaternized polyvinyl alcohol, as well as those 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. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone, such as those available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 are.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives, polymeric dimethyldiallylammomium salts, polyquaternium-27 and their copolymers and also polymers of the polyquaternium-2 type. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, and polymers of the polyquaternium type 2, in particular the commercial product Mirapol ^® A-15, are very particularly preferred cationic polymers.

Cationic polymers according to the invention are also cationically derivatized protein hydrolysates, as they are, for example, under the trademarks Lamequat® ^® and Croquat ^® commercially.

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

The combination of the color-retaining polymers with vitamins, provitamins and vitamin precursors and their derivatives has also proven to be advantageous.

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

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

The vitamin B group or the vitamin B complex include u. a.

Vitamin B, (thiamine)

Vitamin B ₂ (riboflavin)

• Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. This is preferred according to the invention Nicotinamide, which is contained in the agents used according to the invention preferably in amounts of 0.05 to 1% by weight, based on the total agent.

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

• Vitamin B ₆ (pyridoxine as well as pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the agents used according to the invention preferably in amounts of 0.1 to 3% by weight, based on the total agent. Use in the form of the palmitic acid ester may be preferred. Use in combination with tocopherols may also be preferred.

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

Vitamin F. The term “vitamin F” usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. The compound (3aS, 4S. 6ai?) - 2-oxohexa- hydrothienol [3,4 - ^ - imidazole-4-valeric acid] is designated as vitamin H, but for which the trivial name biotin has now become established. Biotin is contained in the agents used according to the invention preferably in amounts of 0.0001 to 0.1% by weight, in particular in amounts of 0.001 to 0.01% by weight. The agents used according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, E and H.

Panthenol and its derivatives as well as nicotinamide and biotin are particularly preferred.

Finally, the effect of the color-preserving polymers can also be increased by the combined use with plant extracts.

These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, reference is made in particular to the extracts which are listed in the table beginning on page 44 of the 3rd edition of the guide to the declaration of ingredients of cosmetic products, published by the Industry Association for Personal Care and Detergents (IKW), Frankfurt.

According to the invention, the extracts from green tea, oak bark and nettle are particularly important. 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, common hake, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.

The extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera are particularly preferred. Coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, cuckoo flower, quendel, yarrow, squirrel, meristem, ginseng and ginger root. The extracts from green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon are particularly suitable for the use according to the invention.

Water, alcohols and mixtures thereof can be used as extractants for the production of the plant extracts mentioned. Among the alcohols, lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as ethylene glycol and propylene glycol, are preferred, both as the sole extracting agent and in a mixture with water. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

According to the invention, the plant extracts can be used both in pure and in diluted form. If they are used in dilute form, they usually contain about 2 to 80% by weight of active substance and, as a solvent, the extractant or mixture of extractants used in their extraction.

Furthermore, it may be preferred to use mixtures of several, in particular two, different plant extracts in the agents according to the invention. The color-retaining polymer is preferably applied to the dyed keratin fiber in a separate step either directly after the actual dyeing process or in separate treatments, if appropriate also days or weeks after the dyeing process.

The term dyeing process includes all processes known to the person skilled in the art, in which a dye is applied to the optionally moistened hair and either left on the hair for a time between a few minutes and about 45 minutes and then with water or a surfactant-containing agent is rinsed out or left entirely on the hair. In this context, it is expressly referred to the known monographs, e.g. B. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referring to the corresponding knowledge of the expert. There are no fundamental restrictions with regard to the manner in which the color-preserving polymers according to the invention are applied to the keratinic fiber, in particular human hair. However, preparations remaining on the hair have proven to be particularly effective and can therefore represent preferred embodiments of the teaching according to the invention. According to the invention, “remaining on the hair” means those preparations which are not rinsed out of the hair again after a period of a few seconds to an hour using water or an aqueous solution. Rather, the preparations remain on the hair until the next hair wash, ie generally more than 12 hours.

According to a first preferred embodiment, these preparations are formulated as a hair treatment or hair conditioner. The preparations according to the invention in accordance with this embodiment can be rinsed out with water or an at least predominantly water-containing agent after this exposure time has elapsed; however, as stated above, they are preferably left on the hair.

The way in which these preparations are packaged is in principle not subject to any restrictions. Creams, lotions, solutions, water, emulsions such as W / O, O / W and multiple emulsions, gels, sprays, aerosols and foam aerosols are suitable. These are usually formulated on an aqueous or aqueous-alcoholic basis. Lower alkanols and polyols such as propylene glycol and glycerol are used as the alcoholic component. Ethanol and isopropanol are preferred alcohols. Water and alcohol can be present in the aqueous alcoholic base in a weight ratio of 1:10 to 10: 1. Water and aqueous-alcoholic mixtures which contain up to 50% by weight, in particular up to 25% by weight, of alcohol, based on the alcohol / water mixture, can be preferred bases according to the invention. Because of the often associated restrictions with regard to the other constituents, the formulation in the form of a so-called PIT emulsion may, however, be less preferred. The pH of these preparations can in principle be between 2 and 11. It is preferably between 2 and 7, values from 3 to 5 being particularly preferred. to Setting this pH value can be used practically any acid or base that can be used for cosmetic purposes. Food acids are usually used as acids. Edible acids are those acids that are ingested as part of normal food intake and have positive effects on the human organism. Edible acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. In the context of the invention, the use of citric acid and lactic acid is particularly preferred. Preferred bases are ammonia, alkali metal hydroxides, triethanolamine and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

According to further embodiments, however, the agents according to the invention can also be, for example, cleaning agents such as shampoos, care agents such as rinses, setting agents such as hair setting agents, foam setting agents, styling gels and hair dryer shafts, permanent shaping agents such as permanent wave and fixing agents, and in particular in the context of a permanent wave method or Dyeing process used pre-treatment agents or rinsing.

In addition to the color-retaining polymer which is absolutely necessary according to the invention and the further preferred components mentioned above, these preparations can in principle contain all further components known to those skilled in the art for such cosmetic compositions.

Other active ingredients, auxiliaries and additives are, for example, nonionic surfactants such as, for example, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, alkoxylated triglycerides, such as, in particular, ethoxylated castor oil.

Alk (en) yl oligoglucosides, fatty acid N-alkyl glucamides, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional or narrow homolog distribution. anionic surfactants, in particular 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, soaps and sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono alkyl polyoxyethyl esters with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, zwitterionic surfactants, in particular 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 also the cocoacylaminoethylhydroxyethyl - carboxymethylglycinate, ampholytic surfactants such as N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkylimine odipropionic 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, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers , Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert. Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. As methyl cellulose, hydroxyalkyl cellulose and carboxy methyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, symmetrical and asymmetrical, linear and branched dialkyl 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 and di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether , n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert.-butyl-n-octyl ether, isopentyl ether n-octyl ether and 2-methyl-pentyl-n-octyl ether,

Fatty alcohols, in particular linear and / or saturated fatty alcohols with 8 to 22 C atoms, and monoesters of fatty acids with alcohols with 6 to 24 C atoms, active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, Fruit sugar and lactose, conditioning agents such as paraffin oils, vegetable oils, e.g. B. sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil as well as phospholipids, for example soy lecithin, egg lecithin and cephalins, quaternized amines such as methyl l-alkylamidoethyl-2-alkylimidazolimum 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, other substances for adjusting the pH, such as, for example, α- and ß-

Hydroxy carboxylic acids

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts and bisabolol,

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,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, 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,

Reducing agents such as B. thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants.

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, e.g. B. referred to the above monograph by Kh. Schrader.

Within the framework of the teaching according to the invention, it is also possible, although less preferred, to incorporate the color-retaining polymers directly into the coloring or tinting agents.

The composition of the dye or tint is not subject to any principle

Limitations.

Can as a dye (intermediate)

Oxidation dye or products of the developer and coupler type,

• natural and synthetic direct dyes and

• Precursors of nature-analogous dyes, such as indole and indoline derivatives, and mixtures of representatives of one or more of these groups are used.

Primary aromatic amines with a further free one in the para or ortho position are usually used as oxidation dye precursors of the developer type or substituted hydroxyl or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives. Suitable developer components are, for example, p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1 - (2'-hydroxyethyl) - 2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) ) -p-phenylenediamine, 2- (2,5-diamino-phenoxy) -ethanol, 4-amino-3-methylphenol, 2,4,5, 6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5, 6-triaminopyrimidine, 2-hydroxymethylamino-4-amino-phenol, bis- (4th -aminophenyl) amine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol, bis- (2- hydroxy-5-aminophenyl) methane, 1,4-bis (4-aminophenyl) diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) -N (4-aminophenylamino)) -2-propanol, 4- Amino-2- (2-hydroxyethoxy) phenol, 1, 10-bis (2,5-diaminophenyl) -1, 4,7, 10-tetraoxadecane and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as e.g. B. 4,5-diamino-l- (2'-hydroxyethyl) pyrazole. Particularly advantageous developer components are p-phenylenediamine, p-toluenediamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2,4 , 5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine.

M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as oxidation dye precursors of the coupler type. Examples of such coupler components are m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy -4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-

Trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2 '-hydroxyethyl) amino-2-methylphenol, 3 - (Diethylamino) phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5-

(methylamino) benzene, 3- (ethylamino) -4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and their derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, l-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis- (2,4-diaminophenyl) propane, 2,6-bis- (2-hydroxyethylamino) -l-methylbenzene and l-amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol,

2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 -dimethylpyridine, 2,6-dihydroxy-4-methylpyridine,

2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1,6-dihydroxy-naphthalene, 1.7 -Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxy-naphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomo holin and 6-amino-benzomorpholine,

Quinoxaline derivatives such as 6-methyl-1, 2,3, 4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, l-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Methylenedioxybenzene derivatives, such as, for example, l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

Particularly suitable coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

Direct dyes are usually nitrophenylenediamines, nifroaminophenols, azo dyes, anthraquinones or indophenols. Particularly suitable direct dyes are those with the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 known compounds as well as 1,4-bis- (ß- hydroxyethyl) - amino-2-nitrobenzene, 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino- 6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Directly occurring dyes found in nature include, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten tree bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

It is not necessary that the oxidation dye precursors or the substantive dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, further components may be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

With regard to the dyes which can be used in the hair colorants and tints according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care. Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as volume 7 of the series “Dermato- logy "(Ed .: Ch., Culnan and H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, as well as the" European inventory of cosmetic raw materials ", published by the European Community, available in disk form from Bundesverband Deutscher Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel eV, Mannheim, referred to.

For example, indoles and indolines and their physiologically tolerable salts are used as precursors of nature-analogous dyes. Those indoles and indolines are preferably used which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group. 5,6-Dihydroxyindoline, N-methyl-5, 6-dihydroxyindoline, N-ethyl-5, 6-dihydroxyindoline, N-propyl-5, 6-dihydroxyindoline, N-butyl-5,6- dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline as well as 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6- dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-dihydroxyindoline and N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5 6-dihydroxyindole.

The indoline and indole derivatives in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochlorides, sulfates and hydrobromides, are used. When using dye precursors of the indoline or indole type, it may be preferred to use these together with at least one amino acid and / or at least one oligopeptide. Preferred amino acids are amino carboxylic acids, in particular α-amino carboxylic acids and ω-amino carboxylic acids. Arginine, lysine, ornithine and histidine are again particularly preferred among the α-aminocarboxylic acids. A very particularly preferred amino acid is arginine, in particular in free form, but also used as the hydrochloride.

Hair dyes, especially if the coloring is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually weakly acidic to alkaline, i.e. H. adjusted to pH values in the range from about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-l, 3-propanediol, 2-amino-2-ethyl-l, 3-propanediol, 2-amino-2 -methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides. Monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are particularly preferred in this group. It is also possible to use ω-amino acids such as ω-aminocaproic acid as an alkalizing agent.

If the actual hair colors are formed as part of an oxidative process, customary oxidizing agents, such as in particular hydrogen peroxide or its adducts with urea, melamine or sodium borate, can be used. However, oxidation with atmospheric oxygen as the only oxidizing agent can be preferred. It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for enhancing the action of a small amount of oxidizing agents present. The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase and laccase are preferred, but also gluco- seoxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is then expediently mixed with the preparation with the dye precursors immediately before dyeing the hair. The resulting ready-to-use hair color preparation should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C., preferably at the temperature of the scalp. After an exposure time of approx. 5 to 45, in particular 15 to 30, minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. B. a coloring shampoo was used.

In the case of hair that is difficult to color, the preparation with the dye precursors can be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if necessary after an intermediate rinse. After a further exposure time of 10 to 20 minutes, rinsing is then carried out and, if desired, re-shampooing. In this embodiment, according to a first variant, in which the previous application of the dye precursors is said to bring about better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, air oxidation is initially aimed for, the agent applied preferably having a pH of 7 to 10. In the subsequent accelerated postoxidation, the use of acidified peroxidisulfate solutions as the oxidizing agent can be preferred.

Regardless of which of the above-mentioned procedures is chosen in the context of the method according to the invention, the formation of the color can be supported and increased by adding certain metal ions to the agent. Such Metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. In principle, the metal ions can be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

The invention also relates to agents for improving the fastness to washing of colored fibers, in particular keratinic fibers, which are a combination of

- anionic synthetic color-preserving polymer

- a protein hydrolyzate and

- contain a cationic surfactant.

Agents which contain vegetable protein hydrolyzates are preferred.

A third subject of the invention is a process for dyeing fibers, in particular keratin fibers, in which the fibers are dyed in a conventional manner in a first step and an agent is applied to the fibers in a second step which corresponds to at least one synthetic polymer contains one of claims 1 to 7 to increase the wash-fastness of the dyeing, the agent being rinsed out again after an exposure time of 1 to 5 minutes, if desired.

Finally, a fourth object of the invention is a process for dyeing fibers, in particular keratinic fibers, in which in a first step an agent is applied to the fibers that contains at least one synthetic polymer according to one of claims 1 to 7 to increase the wash-fastness of the dyeing contains, and then in a second step the fibers are dyed in the usual way. In the context of this method, it may be preferred to apply the first agent in the form of a spray. formulation Examples

Unless otherwise noted, all quantities are parts by weight.

1. Hair conditioner

Eumulgin ^® B2 ¹ 0.3

Cetyl / stearyl alcohol 3.3

Isopropyl myristate 0.5

Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart ^® A-CA ² 2.0

Salcare ^® SC 96 ³ 1.0

Citric acid 0.4

Phenonip® ⁴ 0.8

Water ad 100

Cetylstearyl alcohol + 20 EO (INCI name: Ceteareth-20) (HENKEL) trimethylhexadecylammonium chloride (approx. 25% active substance in water; INCI name: Aqua, Cetrimonium Chloride)

N, N, N-trimemyl-2 [(methyl-l-oxo-2-propenyl) oxy] -ethanaminium chloride homopolymer (50% active substance; INCI name: Polyquaternium-37 (and) propylene glycol dicaprilate dicaprate ( and) PPG-1 Trideceth-6) (ALLIED COLLOIDS) Hydroxybenzoic acid methyl ester-hydroxy ^ hydroxybenzoic acid ethyl ester-hydroxybenzoic acid propyl ester-hydroxybenzoic acid butyl ester-phenoxyethanol mixture (approx. 28% active substance; INCI name: phenoxyethyl, methylparaben, methylparaben, Butyl paraben) (NIPA)

2. Hair conditioner

Eumulgin ^® B2 0.3

Cetyl / stearyl alcohol 3.3

Isopropyl myristate 0.5 Paraffin oil perliquidum 15 cSt. DAB 9 0.3

Dehyquart ^® L 80 ⁵ 0.4

Sepigel ^® 305 ⁶ 1.5

Citric acid 0.4

Phenonip ^® 0.8

Water ad 100

Bis (cocoylethyl) hydroxyethyl methyl ammomum methosulfate (approx. 76% active substance in propylene glycol; INCI name: dicocoylethyl hydroxyethylmonium methosulfate, propylene glycol) (HENKEL)

Copolymer of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (INCI name: polyacrylamide (and) C _I3 -C ₁₄ isoparaffin (and) Laureth-7) (SEPPIC)

3. Hair treatment (rinse off)

Dehyquart ^® F75 ⁷ 4.0

Cetyl / stearyl alcohol 4.0

Paraffin oil perliquidum 15 cSt DAB 9 1.5

Dehyquart® ^® A-CA 4.0

Salcare ^® SC 96 1.5

Gluadin ^® W 20 ⁸ 3.0

Citric acid 0.15

Phenonip ^® 0.8

Water ad 100

Fatty alcohols-methylfriethanolan monium methyl sulfate dialkyl ester mixture (INCI name: distearoylethyl hydroxyethyl monium methosulfate, cetearyl alcohol) (HENKEL)

Wheat protein hydrolyzate (20% active substance in water; INCI name: Aqua (and) Hydrolized Wheat Protein (and) Sodium Benzoate (and) Phenoxyethanol (and) Methylparaben (and) Propylparaben) (HENKEL) 4. Hair treatment (rinse off)

Dehyquart ^® L80 2.0

Cetyl / stearyl alcohol 6.0

Paraffin oil perliquidum 15 cSt DAB 9 2.0

Rewoquat ^® W 75 ⁹ 2.0

Sepigel ^® 305 3.5

Gluadin ^® W 20 3.0

Citric acid 0.15

Phenonip ^® 0.8

Water ad 100

1 -Methy 1-2-nortalgalky 1-3 -talgfettsäijjeamidoethylimidazolimum methosulfate (approx. 75% active substance in propylene glycol; INCI name: Quaternium-27, propylene glycol) (WITCO)

5. Hair treatment (remaining on the hair) Dehyquart ^® F75 0.3

Salcare ^® SC 96 5.0

Dow ^Corning® 200 Fluid, 5 cSt. ¹⁰ 1.5

Gafquat ^® 755N ^and 1.5

Biodocarb ^® 0.02

Perfume oil 0.25

Water ad 100

¹⁰ polydimethylsiloxane (INCI name: Dimethicone) (DOW CORNING)

¹¹ Dimethylaminoethyl methacrylate-vinylpyrrolidone copolymer, quaternized with diethyl sulfate (19% active substance in water; INCI name: Polyquaternium-

11)

(GAF)

12 3-iodo-2-propynyl-n-butyl carbamate (INCI name: iodopropynyl butyl carbamate) (MILKER & GRÜNING) 6. Hair treatment (remaining on the hair) Sepigel ^® 305 5.0

Dow Corning ^® Q2-5220 ¹³ 1.5

Genamin DSAC ^® ¹⁴ 0.3

Phenonip ^® 0.8

Perfume oil 0.25

Water ad 100

¹³ silicone glycol copolymer (INCI name: Dimethicone Copolyol) (DOW CORNING)

¹ dimethyldistearylammonium chloride (INCI name: Distearyldimonium Chloride) (CLARIANT)

Claims

Patentansprtiche

1. Use of a synthetic polymer whose 0.75% preparation in water at 20 ° C has a viscosity of at least 10,000 mPas to improve the wash fastness of dyeings of fibers, in particular keratin fibers.

2. Use according to claim 1, characterized in that the polymer is an anionic polymer which has carboxylate and / or sulfonate groups.

3. Use according to claim 2, characterized in that the anionic polymer contains 2-acrylamido-2-methylpropanesulfonic acid as a monomer, the sulfonic acid group being able to be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt.

4. Use according to claim 2 or 3, characterized in that the anionic polymer is a copolymer of at least one anionic monomer and at least one nonionic monomer.

5. Use according to claim 4, characterized in that the anionic polymer is a copolymer consisting of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as Sodium, potassium, ammonium, mono- or triethanolammonium salt is present.

6. Use according to claim 1, characterized in that the polymer is a cationic polymer which has quaternary ammonium groups.

, Use according to claim 6, characterized in that the cationic polymer is selected from homopolymers of the general formula (I),

R ¹

I

- [CH ₂ -C-] _n X- (I)

I

CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ⁴ are selected independently of one another from C _M alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (I) and nonionic monomer units.

8. Use according to one of claims 1 to 7, characterized in that the synthetic polymer is used in combination with a protein hydrolyzate or a derivative of a protein hydrolyzate.

9. Use according to claim 8, characterized in that the protein hydrolyzate or derivative of the protein hydrolyzate is of vegetable origin.

10. Use according to one of claims 1 to 9, characterized in that the synthetic polymer is used in combination with a cationic surfactant.

11. Use according to one of claims 1 to 10, characterized in that the synthetic polymer is used in combination with a vitamin, a provitamin, a vitamin precursor or a derivative thereof.

12. Use according to one of claims 1 to 11, characterized in that the synthetic polymer is used in combination with a plant extract.

13. Agent for improving the fastness to washing of colored fibers, in particular keratinic fibers, characterized in that it contains a combination of an anionic synthetic polymer according to claim 2, a protein hydrolyzate and a cationic surfactant.

14. Composition according to claim 13, characterized in that the protein hydrolyzate is a vegetable protein hydrolyzate.

15. A process for dyeing fibers, in particular keratin fibers, characterized in that in a first step the fibers are dyed in the usual way and in a second step an agent is applied to the fibers which contains at least one synthetic polymer according to one of claims 1 to 7 to increase the wash-fastness of the dyeing, the agent being rinsed out if desired after an exposure time of 1 to 5 minutes.

16. A process for dyeing fibers, in particular keratin fibers, characterized in that in a first step an agent is applied to the fibers, which contains at least one synthetic polymer according to one of claims 1 to 7 to increase the washfastness of the dyeing, and then in a second step, the keratin fibers are dyed in the usual way.