EP1492492A1 - Method for creating shape memory effects on hair by combining shape memory polymers with cationic active ingredients - Google Patents

Abstract

The invention relates to a method for achieving a retrievable reshaping of the hair. According to the invention, a preparation containing at least one first active ingredient or active ingredient complex is applied to the hair. Said preparation alone or in combination with other substances can give the hair a shape-memory effect once it has been applied to the hair and has undergone the inventive treatment. The preparation also contains at least one second active ingredient, which is a cationic substance. The hair is given a specific (permanent) style and said permanent style is fixed by inducing a chemical or physical modification to the applied active ingredients. After a desired or undesired deformation of the memory shape, the original memory shape can be reproduced by a physical stimulation. In addition to the permanent hairstyle, a second (temporary) style can be imprinted. The invention also relates to a method for reproducing a previously programmed, permanent hairstyle, which has been temporarily reshaped or deformed in another manner into a temporary style.

Description

METHOD FOR PRODUCING SHAPED MEMORY EFFECTS ON HAIR BY COMBINING SHAPED MEMORY POLYMERS WITH CATIONACTIVE ACTIVE SUBSTANCES

The present invention relates to a method for achieving a retrievable hair styling using combinations of cationically active substances and active substances which impart a shape memory effect to the hair, in particular shape memory polymers or macromers which can be crosslinked to shape memory polymers.

10

When shaping hair, a distinction is generally made between temporary and permanent, permanent hair shaping. Temporary hair shaping is usually done using compositions based on solutions or

15 dispersions of hair-fixing polymers. Such products give the hair more or less hold, volume, elasticity, bounce and shine through the addition of polymer. These styling products facilitate e.g. as a gel the shaping and creation of the hairstyle, as a hairspray improve the state of one

20 created hairstyle and increase the volume of the hair as a setting foam. It is disadvantageous that the desired effects are only of relatively short duration and are quickly lost again due to external influences such as combing, wind, high air humidity or contact with water. Permanent hair shaping takes place in the

25 rule by permanent wave treatment. Here are

Disulfide bonds in the hair are reductively split, the hair is given a new shape and fixed by oxidative formation of new disulfide bonds. The disadvantage is that due to the chemical treatment of the hair with reducing and oxidizing agents

30 Impairment of the hair structure cannot be avoided. Another disadvantage of the previously known methods for hair reshaping is that it is not possible to undo a reshaping in a relatively simple manner, ie to move from one hairstyle shape to another without complex new creation. JP 04-41416 discloses hair cosmetics which contain certain linear polyurethanes with a glass transition temperature Tg of 40-90 ° C. The method for hair treatment described corresponds to a treatment with a typical thermoplastic. After applying the composition, the hairstyle shape is created above Tg and fixed by cooling below Tg. When heated again above Tg, the polymer softens and a new hairstyle can be created. A method for a retrievable, reversible hair styling is not described.

The object underlying the present invention was to provide compositions with an improved effectiveness and performance with regard to a retrievable hair shaping with a high degree of restoration of a programmed hairstyle shape. Improved effectiveness or performance can e.g. an improved adhesion to the hair, an improved durability of the effect, higher degrees of restoration of a programmed hairstyle form, etc. Another task was to develop a process for

To make available, with which it is possible to achieve permanent hair shaping without damaging intervention in the hair structure. Another task was to provide a method which makes it possible to undo temporary reshapings several times in a simple manner and with a high level

Accuracy to return to a previously created, programmed, permanent hairstyle shape. Another object was to provide a method which enables deformations of a hairstyle attributable to external influences to be reversed in a simple manner and with high accuracy and to return to a previously created, programmed, permanent hairstyle shape. The object is achieved by a method for hair treatment, wherein

an active substance composition is applied to the hair, the active substance composition containing at least a first active substance or first active substance complex, which are selected or formed from substances which, alone or in combination with further substances, are capable of being applied to hair and after Carrying out the treatment described below to give the hair a shape memory effect, and wherein the active substance composition contains at least one second active substance, which is selected from cation-active substances; before, at the same time or after the application of the active substance composition, the hair is brought into a specific shape (permanent memory form) and then the memory form is fixed by inducing a chemical or physical change in the applied active substances; wherein after an intentional or unwanted deformation of the shape of the memory, the original shape of the memory can essentially be restored by physical stimulation.

One embodiment relates to a method for hair treatment using an active ingredient composition which contains at least two substances which individually have no or only weak shape memory properties and which, when used together in accordance with the method according to the invention, give hair a synergistically increased shape memory effect. Here, the at least two substances can either comprise the above-mentioned first active substance and the above-mentioned, cation-active second active substance or the at least two substances form the above-mentioned active substance complex. A particular embodiment relates to a method for

Hair treatment, being

- the first active ingredient applied to the hair

Composition is a crosslinkable macromer, which forms a shape memory polymer after crosslinking, the macromer containing a) crosslinkable areas that can be crosslinked by chemical bonds and b) thermoplastic areas that are not chemically crosslinkable, - before, at the same time or subsequently the hair in a specific (permanent) shape is brought and then the shape is fixed by chemical crosslinking of the macromer to form the shape memory polymer, the shape memory polymer having at least one transition temperature Ttrans.

Another object of the invention is a method for embossing a second hairstyle shape on a programmed, retrievable first hairstyle shape. Here, a hairstyle (permanent shape) programmed by the above-mentioned method is first heated to a temperature above Ttrans. The hair is then brought into the desired second (temporary) shape and the second shape is fixed by cooling to a temperature below Ttrans.

Another object of the invention is a method for restoring a first hairstyle (permanent shape) previously programmed by the above-mentioned method. For this purpose, a hairstyle in a temporary shape or a hairstyle deformed by cold deformation is heated to a temperature above Ttrans.

Shape memory polymers in the sense of the invention are polymers from which materials can be produced with the property that can be imprinted on them in any shape (permanent shape), into which they can spontaneously transform back after deformation or after being impressed with a second shape (temporary shape) and without external force, simply by heating or by another energetic stimulus. Deformation and

Reconstruction (recovery) is possible several times. The degree to which the original, permanent form is achieved is generally somewhat lower in a first relaxation cycle, consisting of deformation and re-transformation, than in subsequent cycles, presumably because of the removal of defects, textures, etc. which are still present at the beginning. A particularly high degree of re-conversion becomes but then achieved in the subsequent relaxation cycles. The degree of reconversion is preferably at least 30% in the first relaxation cycle, particularly preferably at least 50% and in the subsequent ones

Relaxation cycles preferably at least 60%, particularly preferably at least 80%. But it can also be 90% and more. The degree of reconversion can be measured, as in the case of conventional curl retention measurements, by simply measuring the length of a treated lock of hair or by known, suitable tension-stretching experiments. The shape memory effect of hair is the property that a certain hairstyle shape (permanent memory shape) after a deformation can be restored spontaneously and without external force by simply heating or by another energetic stimulus, i.e. in a first relaxation cycle preferably at least 30%, particularly preferably at least 50% and in the subsequent relaxation cycles preferably at least 60%, particularly preferably at least 80% or 90%.

Macromers or prepolymers which can be crosslinked to form shape memory polymers in the context of the invention are polymers or oligomers in which an impressed permanent shape is fixed in that individual polymer or oligomer strands are formed by chemical bonds be linked together. Crosslinking via chemical bonds can take place via ionic or covalent bonds. The crosslinking reaction can be any chemical reaction, for example a salt formation reaction, a condensation reaction, an addition reaction, a substitution reaction or a radical or photochemically induced reaction. The crosslinking reaction can be carried out using suitable catalysts or initiators or without a catalyst. It can be triggered by a suitable energy source, for example by electromagnetic radiation, ultrasound, heat or mechanical energy. A combination of two or more starting methods can optionally be used to increase the efficiency or the speed of the crosslinking reaction.

Shape memory polymers suitable according to the invention have at least one transition temperature Ttrans. This can be a melting temperature T _m or a glass transition temperature Tg. Above T trans, the polymer has a lower modulus of elasticity than below Ttrans- ^Since s lower ratio of the elasticity modules and above ^st Ttrans i preferably at least 20. The transition temperature Ttrans i ^st preferably greater than room temperature (20 ° C), especially at least 30 ° C, particularly preferably at least 40 ° C and is the temperature above which the spontaneous regression of the permanent form from the deformed or from the temporary form takes place.

Hairstyle or hairstyle form in the sense of the invention is to be understood broadly and includes, for example, the degree of curl or the degree of smoothness of hair. A programmed hairstyle in the sense of the invention is a collection of hair that has a certain shape due to cross-linked shape memory polymers that are fixed in a permanent shape. Restoring a programmed hairstyle in the sense of the invention means that the programmed hairstyle after a deformation again preferably to at least 60%, particularly preferably at least 80%, based on the shape that arises after a first relaxation cycle. The degree of restoration can take place, for example, by measuring the length of a lock of hair or a strand of hair.

Suitable macromers or prepolymers which can be chemically crosslinked to form memory polymers are macromonomers which can be polymerized or crosslinked by individual chemical bonds. The chemically crosslinked polymers are also referred to in WO 99/42147 as thermoset polymers. The macromers and thermoset polymers described in WO 99/42147 are suitable according to the invention and form part of this / application. Soft, thermoplastic segments (switching segments) with a transition temperature Ttrans are cross-linked by chemical, preferably covalent bonds. Switching segments and network points are therefore required, the network points fixing the permanent shape and the switching segments the temporary shape. The shape memory effect is based on the change in elasticity when the Ttrans • D s ratio exceeds or falls below

Elastic modulus below and above Ttrans is preferably at least 20. The greater this ratio, the more pronounced the shape memory effect. There are four types of thermoset polymers with shape memory properties: network polymers, penetrating networks, semi-penetrating ones

Networks and mixed penetrating networks. Network polymers can be formed by covalently linking macromonomers, i.e. of oligomers or polymers with linkable, reactive end groups, preferably ethylenically unsaturated, radical or photochemically reactive

End groups. The crosslinking reaction can be started, for example, by light- or heat-sensitive initiators, by redox systems or their combinations or without initiators, for example by UV light, heat or mechanical energy input. penetrating Networks are made up of at least two components, each of which, however, is not networked with each other. Mixed penetrating networks are formed from at least two components, one component being cross-linked by chemical bonds and another component by physical interactions. Semi-penetrating networks are formed from at least two components, one of which is chemically crosslinkable and the other is not crosslinkable and both components cannot be separated by physical methods.

Fundamentally suitable are all synthetic or natural oligomers and polymers with reactive end or side groups, which give the cross-linked shape memory polymer a suitable transition temperature Ttrans ^and suitable elasticity modules above and below Ttrans, and the end or side groups either during production or afterwards are present in a reactive form through derivatization, which permit a crosslinking reaction using the abovementioned methods. Suitable macromers are, for example, those of the general formula

Al- (X) _n -A2 (I) where AI and A2 are reactive, chemically crosslinkable groups and - (X) n- is a divalent, thermoplastic polymer or oligomer segment. AI and A2 are preferably acrylate or methacrylate groups. The segment (X) n preferably stands for

Polyester, oligoester, polyalkylene glycol, oligoalkylene glycol, polyalkylene carbonate and oligoalkylene carbonate segments, the alkylene groups preferably being ethylene or propylene groups. Suitable macromonomers for the formation of thermoset polymers with shape memory properties are oligo- or poly (ε-caprolactones), oligo- or polylactides, oligo- or polyalkylene glycols, for example polyethylene or polypropylene glycol or their block copolymers, the polymers or oligomers mentioned being terminally or laterally with at least two radically polymerizable, ethylenically unsaturated groups, for example acrylates or methacrylates, are substituted.

The polymer segments can be natural polymers such as e.g. Proteins or polysaccharide derived segments act. They can also be synthetic polymer blocks. Suitable natural polymer segments are proteins such as zein, modified zein, casein, gelatin, gluten, serum albumin or collagen, and also polysaccharides such as alginates, celluloses, dextran, pullulan or polyhyaluronic acid as well as chitin, poly (3-hydroxyalkanoate), in particular poly (β-hydroxybutyrate) ), Poly (3-hydroxyoctanoate) or pol (3-hydroxy fatty acids). Derivatives of natural polymer segments, e.g. alkylated, hydroxyalkylated, hydroxylated or oxidized modifications. Synthetically modified natural polymers are e.g. Cellulose derivatives such as alkyl celluloses, hydroxyalkyl celluloses, cellulose ethers, cellulose esters, nitrocelluloses, chitosan or chitosan derivatives, e.g. can be obtained by N- or / and O-alkyl or hydroxyalkyl substitution. Examples are methyl cellulose, ethyl cellulose, hydroxypropyl cellulose,

Hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, cellulose acetate phthalate, carboxymethylcellulose, cellulose triacetate or cellulose sulfate sodium salt. These are collectively referred to below as "celluloses".

Suitable synthetic polymer blocks are polyphosphazenes, poly (vinyl alcohols), polyamides, polyester amides, polyamino acids, polyanhydrides, polycarbonates, poly (lactide-co-glycolides), polyacrylates, polyalkylenes, polyacrylamides, polyalkylene glycols, polyalkylene oxides, polyalkylene terephthalates, polyorthoesters, polyvinyl ethers, polyvinyl halides, polyvinyl halides , Polyvinylpyrrolidone, polyester, polylactide, polyglycolide, polysiloxane, polyurethane and their copolymers. Examples suitable polyacrylates are poly (methyl methacrylate), poly (ethyl methacrylate), poly (butyl methacrylate), poly (isobutyl methacrylate), poly (hexyl methacrylate), poly (isodecyl methacrylate), poly (lauryl methacrylate), poly (phenyl methacrylate), poly (methyl acrylate),

Poly (isopropyl acrylate), poly (isobutyl acrylate) or poly (octadecyl acrylate). Suitable synthetic, easily biodegradable polymer segments are polyhydroxy acids such as polylactides, polyglycolides and their copolymers, poly (ethylene terephthalate), poly (hydroxybutanoic acid); Poly (hydroxyvaleric acid), - poly [lactide-co- (ε-caprolactone)], - poly [glycolide-co- (ε-caprolactone)], - polycarbonates, poly (amino acids), - poly (hydroxyalkanoates), - polyanhydrides; Polyorthoesters and their mixtures and copolymers. Examples of poorly biodegradable polymer segments are poly (methacrylic acid), poly (acrylic acid), polyamides, polyethylene, polypropylene, polystyrene, polyvinylchloride, polyvinylphenol and their mixtures and copolymers.

In a particularly preferred embodiment, the composition contains a mixture of (A) macromers which are substituted with at least two reactive, crosslinkable groups and (B) macromers which are substituted with only one reactive group. Suitable additional macromers are e.g. those of the general formula

R- (X ') n-A3 (II) where R stands for a monovalent organic radical, A3 for a reactive, chemically crosslinkable group and - (X') n- for a divalent, thermoplastic polymer or oligomer segment. A3 is preferably an acrylate or methacrylate group. The segment (X ') n preferably stands for polyalkylene glycols, their monoalkyl ethers and their block copolymers, the alkylene groups preferably being ethylene or propylene groups and the alkyl groups preferably having 1 to 30 C atoms. Mixtures of (A) are particularly preferably esterified at both ends with acrylic or methacrylic acid

Polyalkylene glycols or polycaprolactones and (B) terminally polyalkylene glycol monoalkyl ethers esterified at one end with acrylic or methacrylic acid, the alkylene groups preferably being ethylene or propylene groups and the alkyl groups preferably being Cl to C30 alkyl groups. Preferred components (A), which can also be used on their own, are: poly (ε-caprolactone) dimethacrylate, poly (DL-lactide) dimethacrylate, poly (L-lactide-co-glycolide) dimethacrylate, poly (ethylene glycol) dimethacrylate, poly (propylene glycol) dimethacrylate, PEG-block-PPG-block-PEG-dimethacrylate, poly (ethylene adipate) dimethacrylate, hexamethylene carbonate dimethacrylate. As component (B) e.g. suitable: poly (ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate and their monoalkyl ether.

Another particular embodiment relates to a method for hair treatment, wherein

- The first active ingredient of the composition applied to the hair is a shape memory polymer which has at least two transition temperatures Ttrans ^and T 'trans and a) at least one hard segment which can be crosslinked by physical interaction and has a first transition temperature T' trans which is above room temperature, preferably more than 10 ° C above room temperature, and b) at least one soft segment with a second

Transition temperature Ttrans which is below T 'trans, preferably at least 10 ° C below T' trans, before, simultaneously or subsequently, the hair is brought into a specific (permanent) shape and then the shape is fixed by physical crosslinking of the shape memory polymers becomes. The shaping of the hair is expediently carried out with heating to a temperature of at least T 'trans, ^and the hair shape is transixed by cooling to a temperature below' T '. Room temperature usually means ambient temperature, preferably at least 20 ° C, in warmer climates preferably at least 25 ° C. The composition can be applied to the hair in various ways, for example directly by spraying or indirectly by first applying it to the hand or to a suitable auxiliary such as, for example. Comb, brush etc. and then spread it in or on the hair. The consistency of the composition can be, for example, that of a solution, dispersion, lotion, thickened lotion, gel, foam, a semi-solid mass, creamy or waxy.

Another object of the invention is a method for

Applying a second hairstyle to a programmed, retrievable first hairstyle. Here, a hairstyle (permanent shape) programmed by the above-mentioned method is first heated to a temperature between T 'trans ^{and < τ} trans. The hair is then brought into the desired second (temporary) shape and the second shape is fixed by cooling to a temperature below Ttrans.

Another object of the invention is a method for restoring a first hairstyle (permanent shape) previously programmed by the above-mentioned method. For this purpose, a hairstyle in a temporary shape or a hairstyle deformed by cold deformation is heated to a temperature above Ttrans. The permanent form regresses spontaneously and automatically. Cold shaping of a hairstyle means a hairstyle change at ambient temperature without the addition of additional heat by a hair dryer or similar devices. The deformation can be caused mechanically, for example by simply unhooking the curls underneath Gravity, by combing or brushing the hair, by wind or moisture, by mechanical influences while sleeping or lying etc.

The invention also relates to a method for reprogramming a permanent hairstyle shape previously programmed according to the above-mentioned method into another, new permanent shape. For this purpose, the original hairstyle is heated to a temperature above T 'trans and the hair is brought into a new shape. Then the new shape is fixed by cooling to a temperature below T 'trans.

For the purposes of the invention, physically crosslinkable shape memory polymers are polymers in which the impressed permanent shape is fixed by crosslinking on the basis of physical interactions. Cross-linking through physical interactions can take place in that certain segments of the polymer chains assemble into crystalline areas. The physical interactions can be charge transfer complexes, hydrogen bonds, dipolar or hydrophobic interactions, van der Waals interactions or ionic interactions of polyelectrolyte segments. The interactions can take place between different segments within a polymer strand (intramolecular) and / or between different polymer strands (intermolecular). The interactions can be formed, for example, by cooling (in particular in the case of crystallizations) and / or by drying, i.e. can be triggered by removing solvents.

Physically crosslinkable shape memory polymers suitable according to the invention have at least two transition temperatures ^τ trans ^and T 'trans. Both transition temperatures can be, for example, melting temperatures T _m or glass Act transition temperatures Tg. The polymer has a lower modulus of elasticity above Ttrans than below Ttrans. The ratio of the elastic moduli below and above Ttrans is preferably at least 10, particularly preferably at least 20. The lower transition temperature trans is preferably greater than room temperature (20 ° C.), in particular at least 30 ° C., particularly preferably at least 35 ° C. or at least 40 ° C., and is the temperature above which the spontaneous regression of the permanent shape from the deformed or from the temporary shape occurs. Ttrans is preferably so far above the usual ambient temperatures that no significant, unintended, thermally induced deformation of the temporary hairstyle shape occurs at ambient temperature. Suitable ranges for Ttrans are, for example, from 25 to 100 ° C, from 30 to 75 ° C, from 35 to 70 ° C or from 40 to 60 ° C. The upper transition temperature T 'rans is above Ttrans ^and i is the temperature above which the permanent shape is embossed or the permanent shape is embossed into a new permanent shape and below which the permanent shape is fixed. T 'trans is preferably so far above trans »that when the hairstyle is heated to a temperature above Ttrans ^to restore the permanent hairstyle shape or to create a temporary hairstyle shape while maintaining the permanent hairstyle shape, no significant, unintentional, thermally induced deformation of the permanent hairstyle shape occurs. T ¹ trans is preferably at least 10 ° C, particularly preferably at least 20 ° C or at least 30 ° C above Ttrans. The difference between T ¹ trans and Ttrans can be, for example, from 10 to 80 ° C, from 20 to 70 ° C or from 30 up to 60 ° C. Suitable ranges for trans are, for example, from 40 to 150 ° C., from 50 to 100 ° C. or from 70 to 95 ° C.

Suitable physically cross-linked shape memory polymers are polymers which consist of at least one hard segment and at least one consist of a soft segment. The hard segment has physical crosslinks and has a transition temperature T 'trans - which is above room temperature, preferably more than 10 ° C. above 20 ° C. The soft segment has a transition temperature T trans which is below T ¹ trans ', preferably at least 10 ° C. below T' trans. The polymer segments are preferably oligomers, in particular linear chain molecules with a molecular weight of, for example, 400 to 30,000, preferably 1000 to 20,000 or 1,500 to 15,000. They can be linear di, tri, tetra or multiblock copolymers, branched, dendritic or grafted copolymers , They are preferably not linear polyether urethanes which contain bis (2-hydroxyethyl) hydroquinone. The molecular weight of the polymers can be, for example, from 30,000 to 1,000,000, preferably from 50,000 to 700,000 or from 70,000 to 400,000. Suitable physically cross-linked shape memory polymers are described in WO 99/42147 and are referred to there as thermoplastic polymers. The thermoplastic polymers described in WO 99/42147 and the production methods described therein are suitable according to the invention and form part of this application. You assign one

Degree of crystallinity of preferably 3 to 80%, particularly preferably 3 to 60%. The ratio of the elastic modulus above and below Ttrans is preferably at least 10, particularly preferably at least 20. The polymer segments can be natural polymers such as e.g. Proteins or polysaccharide derived segments act. They can also be synthetic polymer blocks. Suitable natural or synthetic polymer segments are the same as those mentioned above for the crosslinkable macromers.

Suitable shape memory polymers are in particular multiblock copolymers which have at least one first type of blocks and at least one different second type of blocks with the blocks causing the multiblock copolymer to have two different transition temperatures. Suitable multiblock copolymers are, in particular, those which are produced from at least two different macrodiols and at least one diisocyanate. Macrodiols are oligomers or polymers with at least two free hydroxy groups. Oligomers generally consist of at least two, preferably at least three, in particular 4 to 20, 5 to 15 or 6 to 10 monomers. The macrodiols can have the general formula HO-A-OH, where A is a divalent, oligomeric or polymeric group, preferably polyester or oligoester. The diisocyanate can have the general formula OCN-B-NCO, where B is a divalent organic group, preferably an alkylene or arylene group, which can be substituted by further substituents. The alkylene group can be linear, branched or cyclic and preferably has 1 to 30 C atoms, particularly preferably 2 to 20 or 5 to 15 C atoms.

Particularly preferred shape memory polymers are the copolyester urethanes described in WO 99/42147, in particular the reaction products from (a) two different macrodiols, selected from α, ω-dihydroxy-polyesters, α, ω-dihydroxy-oligoesters, α, ω-dihydroxy-polylactones and α, ω-dihydroxy-oligolactones and (b) at least one diisocyanate, preferably trimethylhexane-1,6-diisocyanate. Are particularly preferred

Macrodiols made from poly (para-dioxanone) (PDX), poly (pentadecalactone) (PDL), poly (ε-caprolactone) (PCL), poly (L-lactide-co-glycolide) (PLGA). The molecular weights of the macrodiols are preferably in the range from 400 to 30,000, preferably 1,000 to 20,000 or 1,500 to 15,000. The molecular weights of the resulting multiblock copolymers are preferably M = from 30,000 to 1,000,000, particularly preferably from 50,000 to 700,000 or from 70,000 to 400,000 g / mol, determinable by GPC. The polydispersities are preferably in the range from 1.7 to 2.0. Cation active ingredients

Cationactive substances are distinguished by the fact that they either carry at least one permanently cationic group in the molecule, for example an iminium group or an ammonium group, in particular a quaternary ammonium group, or that they carry at least one group which can be cationized, for example a primary, secondary or tertiary amine group , which can be cationized by protonation, preference being given to quaternary ammonium groups. The cationic active ingredient is a substance which, due to the cationic or cationizable group, has a substantivity to human hair. Suitable cationic substances are e.g. Surfactants with cationic or cationizable groups, especially cationic surfactants, betaine or amphoteric surfactants; Polymers with cationic or cationizable groups, in particular cationic, betaine or amphoteric polymers; Silicone compounds with cationic or cationizable groups, in particular diquaternary or polyquaternary siloxanes or amodimethicones; cationically derivatized proteins; cationically derivatized protein hydrolyzates or betaine.

Suitable cationic surfactants are surfactants which contain both a quaternary ammonium group and a hydrophobic group. These can be cationic or amphoteric, betaine surfactants. Suitable cationic surfactants contain amino groups or quaternized hydrophilic ammonium groups which carry a positive charge in solution and can be represented by the general formula (III),

_N (+) _R 1 _R 2 _R 3 _R 4 _χ (-) _(III) where Rl to R4 independently of one another are aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, Alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 carbon atoms, where at least one radical has at least 8 carbon atoms and X ^{~ represents} an anion, for example a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride. In addition to the carbon atoms and the hydrogen atoms, the aliphatic groups can also contain cross-links or other groups such as, for example, further amino groups.

Examples of suitable cationic surfactants are the chlorides or bromides of alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, e.g. Cetyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, the dialkyldimethylammonium chlorides or bromides, alkyl pyridinium salts, e.g. Lauryl or cetyl pyridinium chloride, alkyl amidoethyl trimethyl ammonium ether sulfates and compounds with a cationic character such as amine oxides, e.g. Alkyl methyl inoxides or alkyl inoethyldimethylamine oxides. Cetyltrimethylammonium chloride is particularly preferred.

Suitable amphoteric surfactants are derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds of the formula (IV)

(R ⁶ ) χ

R ⁵ -γ ⁽ + ⁾ -CH ₂ -R ⁷ -Z ^(_) (IV) where R5 is a straight-chain or branched-chain alkyl, alkenyl or hydroxyalkyl group with 8 to 18 C atoms and 0 to about 10

Represents ethylene oxide units and 0 to 1 glycerol unit; Y is a group containing N, P or S; R6 is an alkyl or monohydroxyalkyl group with 1 to 3 C atoms; X is 1 if Y is a sulfur atom and X is 2 if Y is a sulfur atom Is nitrogen atom or a phosphorus atom; R7 is an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms and Z ^ ^~ 'represents a carboxylate, sulfate, phosphonate or phosphate group.

Other amphoteric surfactants such as betaines are also suitable for the hair treatment composition according to the invention. Examples of betaines include C8 to C18 alkyl betaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and laurylbis (2-hydroxypropylbetaine) alphacarboxy; C8 to C18 sulfobetaines such as cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, laurylbis- (2-hydroxyethyl) sulfopropylbetaine; the carboxyl derivatives of imidazole, the C8 to C18 alkyldimethylammonium acetates, the

C8 to C18 alkyldimethylcarbonylmethylammonium salts and the C8 to C18 fatty acid alkylamido betaines such as e.g. the coconut fatty acid amidopropyl betaine and the N-

Coconut fatty acid amidoethyl-N- [2- (carboxymethoxy) ethyl] glycerol (CTFA name: Cocoamphocarboxyglycinate) and cocamidopropyl hydroxysultaine.

The suitable cationic polymers are preferably hair-setting or hair-conditioning polymers. Suitable polymers preferably contain quaternary amine groups. The cationic polymers can be homopolymers or copolymers, the quaternary nitrogen groups being contained either in the polymer chain or preferably as a substituent on one or more of the monomers. The monomers containing ammonium groups can 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, for example Trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic, cationic nitrogen-containing groups such as pyridinium, imidazolium or quaternary pyrrolidones, for example alkylvinylimidazolium, alkylvinylpyridinium, or

Alyklvinylpyrrolidon salts. The alkyl groups of these monomers are preferably lower alkyl groups such as e.g. Cl to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups.

The monomers containing ammonium groups can be copolymerized with non-cationic monomers. Suitable comonomers are, for example, acrylamide, methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl caprolactam, vinyl pyrrolidone, vinyl esters, e.g. Vinyl acetate, vinyl alcohol,

Propylene glycol or ethylene glycol, where the alkyl groups of these monomers are preferably Cl to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups.

Suitable polymers with quaternary amine groups are, for example, the polymers described in the CTFA Cosmetic Ingredient Dictionary under the names Polyquaternium, e.g. Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-9, Polyquaternium-10, quaternized

Vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (Polyquaternium-11), Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Methyl-vinylimidazolium chloride / Vinylpyrrolidon Copolymer (Polyquaternium-16), Polyquaternium-18, Polyquaternern Polyquaternium-20, Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29, Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-42, Polyquaternium-43, Polyquaternium-44, Polyquaternium-45, Polyquaternium-46, Polyquaternium-47, Polyquaternium-48, Polyquaternium-49, Polyquaternium-50, 51, polyquaternium-52, polyquaternium-53,

Polyquaternium-54, Polyquaternium-55, Polyquaternium-56. Quaternary silicone polymers or oligomers such as e.g. Silicone polymers with quaternary end groups (Quaternium-80). Of the cationic polymers which can be contained in the agent according to the invention, e.g.

Vinylpyrrolidone / dimethylaminoethyl methacrylate methosulfate copolymer, which is sold under the trade names Gafquat 755 N and Gafquat 734 and of which Gafquat 755 N is particularly preferred, is suitable. Further cationic polymers are, for example, the copolymer of polyvinylpyrrolidone and sold under the trade name LUVIQUAT HM 550

Imidazolimine, that sold under the trade name Merquat Plus 3300 terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide, sold under the trade name Gaffix ^® VC 713 terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam, and the product sold under the trade name Gafquat HS 100 vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer. Cationic polyurethanes, for example formed from at least one organic diisocyanate and at least one organic dihydroxy compound substituted with at least one quaternary ammonium group, are also suitable - in addition, nonionic organic dihydroxy compounds can also be copolymerized.

Suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example cationic derivatives of cellulose, starch or guar. Chitosan and chitosan derivatives are also suitable. Cationic polysaccharides have the general formula (V) G-0-BN ⁺ R ^a R ^b R ^c X ^" (V) 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 and R ^c are independently of one another alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having up to 18 carbon atoms, the total number of carbon atoms in R ^a , R ^b and R ^c preferably being a maximum of 20 ; X is a common counter anion, has the same meaning as in formula (III) and is preferably chloride. A cationic cellulose is sold under the name Polymer JR and has the INCI name Polyquaternium-10. Another cationic cellulose has the INCI name Polyquaternium-24 and is sold under the trade name Polymer LM-200. A suitable cationic guar derivative is sold under the trade name Jaguar R and has the INCI name Guar Hydroxypropyltrimonium Chloride.

Particularly preferred cationic substances are chitosan,

Chitosan salts and chitosan derivatives. The chitosans to be used according to the invention are completely or partially deacetylated chitins. The production of chitosan is preferably based on the chitin contained in the shell remains of crustaceans, which is available in large quantities as a cheap and natural raw material. The molecular weight of the chitosan can be distributed over a broad spectrum, for example from 20,000 to about 5 million g / mol. For example, low molecular weight chitosan with a molecular weight of 30,000 to 70,000 g / mol is suitable. However, the molecular weight is preferably above 100,000 g / mol, particularly preferably from 200,000 to 700,000 g / mol. The degree of deacetylation is preferably 10 to 99%, particularly preferably 60 to 99%. A suitable chitosan is sold, for example, under the trade name Flonac. It has a molecular weight of 300,000 to 700,000 g / mol and is 70 to 80% deacetylated. A preferred chitosan is Chitosoniu pyrrolidonecarboxylate which is for example marketed under the name Kytamer ^® PC. The chitosan contained has a molecular weight of approx. 200,000 to 300,000 g / mol and is 70 to 85% deacetylated. Quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethyl or hydroxybutyl chitosan, are suitable as chitosan derivatives.

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%, particularly preferably between 70 and 100%, based on the number of free base groups. In principle, all cosmetically compatible inorganic or organic acids can be used as neutralizing agents, for example formic acid, tartaric acid, malic acid, lactic acid, citric acid, pyrrolidone carboxylic acid, hydrochloric acid and others, of which pyrrolidone carboxylic acid is particularly preferred.

Preferred polymers are those which have sufficient water or alcohol solubility to be present in the agent according to the invention in completely dissolved form. The cationic charge density is preferably 1 to 7 meq / g.

Suitable cationic silicone compounds preferably have either at least one amino group or at least one ammonium group. Suitable silicone polymers with amino groups are known under the INCI name Amodimethicone. These are polydimethylsiloxanes with aminoalkyl groups. The aminoalkyl groups can be side or terminal. Suitable aminosilicones are those of the general formula (VI) R ⁸ R ⁹ R ¹⁰ Si- (OSiR ¹¹ R ¹² ) x- (OSiR ¹³ Q) y-OSiR ¹⁴ R ¹⁵ R ¹⁶ (VI) R ⁸ , R, R and R are independently the same or different and mean Cl- to CIO-alkyl, phenyl, hydroxy, hydrogen, Cl- to ClO-alkoxy or acetoxy, preferably C1-C4-alkyl, particularly preferably methyl;

R and R are independently the same or different and are - (CH2) _a ^_NH 2 ^{where a} is 1 to 6, Cl to ClO alkyl, phenyl, hydroxy, hydrogen, Cl to ClO alkoxy or acetoxy, preferably C1- C4 alkyl, particularly preferably methyl; R ¹¹ , R and R are, independently of one another, the same or different and denote hydrogen, Cl to C20 hydrocarbon, which can contain O and N atoms, preferably Cl to ClO alkyl or phenyl, particularly preferably Cl to bis C4 alkyl, especially methyl; Q means -A-NR ¹⁷ R ¹⁸ , or -AN ⁺ R ¹⁷ R ¹⁸ R ¹⁹ where A stands for a divalent Cl to C20 alkylene connecting group, which can also contain O and N atoms and OH groups, and R , R and R are independently the same or different and are hydrogen, Cl- to C22-hydrocarbon, preferably Cl- to C-4-alkyl or phenyl. Preferred radicals for Q are - (CH ₂ ) 3-NH ₂ , - (CH ₂ ) 3NHCH ₂ CH2NH2,

- (CH2) 3θCH2CHOHCH ₂ NH ₂ and - (CH ₂ ) ₃ N (CH ₂ CH ₂ OH) ₂ , - (CH ₂ ) 3-NH3 ⁺ and - (CH2) ₃ OCH2CHOHCH2N ⁺ (CH ₃ ) 2R ²⁰ , where R ^{20 is} a Cl to C22 alkyl radical, which may also have OH groups. X represents a number between 1 and 10,000, preferably between 1 and 1,000;

Y represents a number between 1 and 500, preferably between 1 and 50.

The molecular weight of the aminosilicones is preferably between 500 and 100,000. The amine content (meq / g) is preferably in the range from 0.05 to 2.3, particularly preferably from 0.1 to 0.5. Suitable silicone polymers with two quaternary ammonium groups are known under the INCI name Quaternium-80. These are dimethylsiloxanes with two terminal aminoalkyl groups. Suitable quaternary aminosilicones are those of the general formula (VII)

_R 21 _R 22 _R 23 _N + _ _A _ _siR 8 _R 9_ (osiR ¹¹ R ¹² ) _n -OSiR ⁸ R ⁹ -AN ⁺ R ²¹ R ²² R ²³ 2X ^~ (VII)

A has the same meaning as given above for formula (VI) and is preferably - (CH ₂ ) ₃ OCH ₂ CHOHCH ₂ N ⁺ (CH ₃ ) ₂ R ²⁰ , where R ^{20 is} a Cl to C22 alkyl radical, which is also May have OH groups;

R ⁸ , R ⁹ , R and R have the same meaning as above

Formula (VI) indicated and are preferably methyl;

R ²¹ , R ²² and R independently of one another are Cl to C22 alkyl radicals which may contain hydroxyl groups and where preferably at least one of the radicals has at least 10 carbon atoms and the remaining radicals have 1 to 4 carbon atoms; n is a number from 0 to 200, preferably from 10 to 100.

Such diquaternary polydimethyl siloxanes are sold, for example, under the trade names Abil ^® Quat 3270, 3272 and 3274.

Other suitable cationic hair care compounds are cationically modified protein derivatives or cationically modified protein hydrolyzates and are e.g. Known 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 hydroxypropyltrimonium

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 hydrolyzates are mixtures of substances which can be obtained, for example, by reacting alkaline, acidic or enzymatically hydrolyzed proteins with glycidyl trialkylammonium salts or 3-halo-2-hydroxypropyl trialkylammonium salts. Proteins that serve as starting materials for the protein hydrolyzates can be of both vegetable and animal origin. usual

Starting materials are e.g. Keratin, collagen, elastin, soy protein, rice protein, milk protein, wheat protein, silk protein or almond protein. The hydrolysis produces mixtures of substances with molecular weights in the range from approximately 100 to approximately 50,000. Usual average molecular weights are in the range from about 500 to about 1000.

The cationically derivatized protein hydrolyzates advantageously contain one or two long C8 to C22 alkyl chains and correspondingly two or one short Cl to C4 alkyl chains. Compounds containing a long alkyl chain are preferred.

Compositions for hair treatment according to the invention contain the first, a shape memory effect of hair alone or in combination with another substance, in an amount of preferably 0.01 to 25% by weight, particularly preferably 0.1 to 15% by weight in one suitable medium.

Preferred amounts for the cationic active ingredients are from 0.01 to 10% by weight, particularly preferably from 0.05 to 5% by weight. The composition can include be present as a solution, dispersion, emulsion, suspension or latex. The liquid, gel-like, semi-solid or solid medium is essentially cosmetically acceptable and physiologically harmless.

The composition according to the invention is generally in the form of a solution or dispersion in a suitable solvent. Aqueous, alcoholic or aqueous-alcoholic solvents are particularly preferred. Suitable solvents are, for example, aliphatic linear or branched Cl to C4 alcohols or a mixture of water with one of these alcohols. However, other organic solvents can also be used, particular mention being unbranched or branched hydrocarbons such as pentane, hexane, isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane, organic linear or cyclic ethers, for example tetrahydrofuran (THF) or liquid organic esters, for example ethyl acetate are. Furthermore, silicone-based solvents are also suitable, in particular silicone oils based on linear or cyclic polydimethylsiloxanes (dimethicone or cyclomethicone). volatile silicones are preferred with boiling points less than 200 ° C. Further solvents are acetone, tetrahydrofuran, chloroform etc. The solvents are preferably in an amount of 0.5 to 99% by weight, particularly preferably in an amount of 10 to 97% by weight, 20 to 95% by weight or 40 up to 90% by weight.

Compositions according to the invention can additionally contain 0.01 to 25% by weight of at least one hair-care, hair-fixing and / or hair-coloring active ingredient. Hair-setting active ingredients are in particular the known, conventional film-forming and hair-fixing polymers. The film-forming and hair-fixing polymer can be of synthetic or natural origin and have nonionic, cationic, anionic or amphoteric character. Such a polymer additive, which can be contained in amounts of 0.01 to 25% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, can also be made from a mixture of several polymers exist and through the

The addition of other polymers with a thickening effect can be modified in its hair-setting properties. According to the invention, film-forming, hair-fixing polymers are understood to mean those polymers which, when used, contain 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution are able to deposit a polymer film on the hair and in this way to strengthen the hair.

Suitable synthetic, nonionic, film-forming, hair-fixing polymers in the hair treatment composition according to the invention are homopolymers of vinylpyrrolidone, homopolymers of N-vinylformamide, copolymers of vinylpyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides, polyvinyl alcohols

Polyethylene glycols with a molecular weight of 800 to 20,000 g / mol are used. Suitable synthetic, film-forming anionic polymers include crotonic acid / vinyl acetate copolymers and terpolymers made from acrylic acid, ethyl acrylate and N-t-butyl acrylamide. Natural film-forming polymers or polymers made therefrom by chemical conversion can also be used in the hair treatment composition according to the invention, e.g. Chinese balsam resin, cellulose derivatives such as hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol, or shellac in neutralized or unneutralized form. Amphoteric polymers can also be used in the hair treatment composition according to the invention. Are suitable for. B. copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters.

The consistency of the hair treatment composition according to the invention can be increased by adding thickeners. Homopolymers of acrylic acid with a

Molecular weight from 2,000,000 to 6,000,000 g / mol suitable. Copolymers of acrylic acid and acrylamide (sodium salt) with a molecular weight of 2,000,000 to 6,000,000 g / mol, sclerotium gum and copolymers of acrylic acid and methacrylic acid are suitable.

A cosmetic agent according to the invention can be used in various application forms, for example in the form of a lotion, a spray lotion, a cream, a gel, a gel foam, an aerosol spray, a non-aerosol spray, an aerosol foam, a non-aerosol foam, an O / W - or W / O emulsion, a microemulsion or a hair wax.

If the hair treatment composition according to the invention is in the form of an aerosol spray, it additionally contains 15 to 85% by weight, preferably 25 to 75% by weight, of a propellant and is filled in a pressure container with a spray head. Lower alkanes, e.g. n-Butane, isobutane and propane, or their mixtures as well as dimethyl ether or fluorohydrocarbons such as F 152a (1, 1-difluoroethane) or F 134 (tetrafluoroethane) as well as gaseous blowing agents such as N2, N2O and CO2 at the pressures under consideration as well as mixtures of the above-mentioned blowing agents.

If the hair treatment composition according to the invention is in the form of a sprayable non-aerosol hairspray, it is sprayed with the aid of a suitable mechanically operated spraying device. Mechanical spraying devices are to be understood as devices which make it possible to spray a composition without using a propellant. A suitable mechanical spray device can be, for example, a spray pump or an elastic container provided with a spray valve, in which the cosmetic agent according to the invention is filled under pressure, the elastic container expanding and from which the agent continuously as a result of the contraction of the elastic container when the spray valve is opened is used. If the hair treatment composition according to the invention is in the form of a hair foam (mousse), then it contains at least one customary, known foaming substance. The agent is foamed with or without the help of propellant gases or chemical propellants and incorporated into the hair as a foam and left in the hair without rinsing. A product according to the invention has a device for foaming the composition as an additional component. Devices for foaming are to be understood as devices which allow the foaming of a liquid with or without the use of a blowing agent. A commercially available pump foamer or an aerosol foam head, for example, can be used as a suitable mechanical foaming device.

If the hair treatment composition according to the invention is in the form of a hair gel, it additionally contains at least one gel-forming substance in an amount of preferably 0.05 to 10, particularly preferably 0.1 to 2% by weight. The viscosity of the gel is preferably from 100 to 50,000 mm / s, particularly preferably from 1,000 to 15,000 mm / s at 25 ° C., measured as a dynamic viscosity measurement using a Bohlin Rheometer CS, measuring body C25 at a shear rate of 50 s.

If the hair treatment composition according to the invention in the form of a

Hair wax is present, it additionally contains water-insoluble fat or wax substances or substances which give the composition a wax-like consistency in an amount of preferably 0.5 to 30% by weight. Suitable water-insoluble substances are, for example, emulsifiers with an HLB value below 7, silicone oils, silicone waxes, waxes (for example wax alcohols, wax acids, wax esters, and in particular natural waxes such as beeswax, carnauba wax, etc.), fatty alcohols, fatty acids, fatty acid esters or high molecular weight polyethylene glycols one Molecular weight from 800 to 20,000, preferably from 2,000 to 10,000 g / mol.

If the hair treatment composition according to the invention is in the form of a hair lotion, it is in the form of an essentially non-viscous or slightly viscous, flowable solution, dispersion or emulsion containing at least 10% by weight, preferably 20 to 95% by weight, of a cosmetically acceptable alcohol in front. In particular, the lower C1 to C4 alcohols commonly used for cosmetic purposes, such as e.g. Ethanol and isopropanol can be used.

If the hair treatment composition according to the invention is in the form of a hair cream, it is preferably in the form of an emulsion and either additionally contains viscosity-imparting ingredients in an amount of 0.1 to 10% by weight or the required viscosity and creamy consistency is achieved by micelle formation with the aid of suitable emulsifiers , Fatty acids, fatty alcohols, waxes etc. in the usual way.

In a preferred embodiment, the agent according to the invention is capable of simultaneously embossing a retrievable hairstyle as well as hair coloring. The agent is then formulated as a coloring hair treatment agent, for example as a color fixer, coloring cream, coloring foam, etc. It then contains at least one coloring substance. These can be organic dyes, in particular so-called direct dyes, or inorganic pigments. The total amount of dyes in the composition according to the invention is about 0.01 to 7% by weight, preferably about 0.2 to 4% by weight. Direct dyes suitable for the agent according to the invention are, for example, triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinone dyes, cationic or anionic dyes. Suitable hair-coloring pigments are colorants which are practically insoluble in the application medium and can be inorganic or organic. Inorganic-organic mixed pigments are also possible. The pigments are preferably not nanopigments. The preferred particle size is 1 to 200 μm, in particular 3 to 150 μm, particularly preferably 10 to 100 μm. Inorganic pigments are preferred.

The hair treatment composition according to the invention preferably additionally contains at least one hair-care substance in an amount of 0.01 to 10, particularly preferably 0.05 to 5% by weight. Preferred hair care substances are oily substances such as e.g. Mineral oils, silicone oils, oily fatty acid esters, vegetable oils etc.

Suitable silicone compounds are e.g. Polydimethylsiloxane (INCI: dimethicone), α-hydro-ω-hydroxypolyoxydimethylsilylene (INCI: dimethiconol), cyclic dimethylpolysiloxane (INCI: cyclomethicone), trimethyl (octadecyloxy) silane (INCI: stearoxy-trimethylsilane), dimethylsiloxane / glycolic siloxane /

Dimethicone copolyol), dimethylsiloxane / aminoalkylsiloxane copolymer with hydroxyl end groups (INCI: amodimethicone), monomethylpolysiloxane with lauryl side chains and polyoxyethylene and / or polyoxypropylene end chains, (INCI: laurylmethicone copolyol), dimethylsiloxane / glycol acyloxy / copolymer: aminoxiloxiloxiloxiloxyl copolymer copolymer, INCI Trimethylsilyl end groups (INCI: trimethylsilylamodimethicone). Preferred silicone polymers are dimethicones, cyclomethicones and dimethiconols. Mixtures of silicone polymers are also suitable, such as a mixture of dimethicone and dimethiconol. The names given in brackets above correspond to the INCI nomenclature (International Cosmetic Ingredients), as they are intended for the labeling of cosmetic active ingredients and auxiliaries. Usually, further known cosmetic additives can be added to the hair treatment composition according to the invention, for example non-setting, nonionic polymers such as polyethylene glycols, non-setting, anionic and natural polymers and mixtures thereof in an amount of preferably 0.01 to 50% by weight. Perfume oils in an amount of 0.01 to 5% by weight, opacifiers such as ethylene glycol distearate in an amount of 0.01 to 5% by weight, wetting agents or emulsifiers, in particular anionic or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid alkanolamides such as the esters hydrogenated castor oil fatty acids in an amount of 0.1 to 30% by weight, and also humectants, coloring substances, light stabilizers, antioxidants and preservatives in an amount of 0.01 to 10% by weight.

FIG. 1 schematically shows the process for producing a permanent hairstyle shape that can be called up. A strand of hair is wound on a winding body and sprayed with a solution according to the invention containing a crosslinkable macromer. By irradiation with a suitable energy source, e.g. The desired permanent shape is fixed with a UV lamp. Finally, the winding body is removed.

Figure 2 shows the deformation of a permanent hairstyle shape and restoration of the permanent shape from the temporary shape.

The curl in the permanent form has the length lo • The curl in the deformed form has the length 1 ±. The curl in the restored form has the length I2 • The

Degree of recovery (recovery) is calculated according to: Recovery = (li - 1 ₂ ) / (li - lo) •

The memory factor, in which both the formability of a permanent hairstyle shape into a temporary shape (shape factor) and the resetting of the permanent shape, can serve as a measure for assessing the shape memory properties of a composition from the temporary form (reset factor, degree of recovery) are taken into account. If a smooth streak is assumed, onto which a curl shape is impressed as a permanent shape and onto which a second, smooth shape is then impressed as a temporary shape, the shape factor can be determined according to the following criteria:

The reset factor can be determined according to the following criteria:

The memory factor M results from the respective form factor f, the maximum form factor F = 4, the respective reset factor r and the maximum reset factor R = 6 according to

M = (f / F) * (r / R) * 100

The memory factor should ideally not be below 25, preferably between 25 and 33.3, particularly preferably between 37 and 100.

The following examples are intended to explain the subject matter of the invention in more detail. Examples

Examples 1-6

Compositions were prepared in accordance with Table 1 (quantities in g). Table 1

^> Polyethylene glycol with a molecular weight of 8000, terminated with

Methacrylic acid esterifies ^la 'polyethylene glycol with a molecular weight of 8000' cationic cellulose, polyquaternium-4 ³ 'polyquaternium-11

⁴ 'cationic copolymer of hydroxethyl ethacrylate / quaternized dimethylaminoethyl methacrylate / dodecyl methacrylate, obtainable by radical copolymerization of the comonomers with AIBN in the ratio 6/77/17.

⁵ 'vinyl caprolactam / vinyl pyrrolidone / dimethylaminopropyl methacrylate copolymer

The transition temperatures Ttrans of the shape memory systems were 55-57 ° C. The memory factor M was determined using the method described above. To produce the permanent shape, a strand of water, 20 cm long, moistened with water is twisted onto a hair roller and the polymer solution is applied (20-30 mg polymer / g hair). The treated strand is fixed for 30 minutes at 70 ° C. under UV light (Examples 1 to 5) or without UV light (Example 6). After cooling to room temperature (about 25 ° C), the hair roller is removed. The curly streak (stamped permanent shape) had a length of about 4.5 cm. To create the temporary shape (eg smooth), the wavy strand is heated to approx. 55 ° C, stretched to its original, full length (20 cm) and up

Cooled to room temperature. To restore the permanent shape, the smooth strand is heated to approx. 55 ° C. At this temperature, the streak contracted spontaneously into a permanent shape (curled). To restore the permanent shape (e.g. smooth), the wavy strand is heated again to 55 ° C, stretched to its full length (20 cm) and cooled to room temperature.

Examples 7 to 16 with crosslinkable macromers The following macromers which can be crosslinked to shape memory polymers are used in the hair treatment compositions below. The macromers are prepared analogously as described in WO 99/42147.

Ml PEG (4k) -DMA, polyethylene glycol with a molecular weight of approx. 4000, esterified twice with methacrylic acid

M2 PEG (8k) -DMA, polyethylene glycol with a molecular weight of approx.

8000, twice esterified with methacrylic acid M3 PEG (lOk) -DMA, polyethylene glycol with a molecular weight of approx. 10000, twice esterified with methacrylic acid M4 PLGA (7k) -DMA, poly (L-lactide-co-glycolide) -dimethacrylate with a molecular weight of approx 7000 M5 PCI (10k) -DMA, poly (ε-caprolactone) -dimethacrylate with a molecular weight of approx. 10000

The following hair treatment compositions were used as described in Example 1 with similar results. Example 7: Hair fixative 2 g Macromer Ml

1.50 g vinyl pyrrolidone / vinyl acetate copolymer 0.20 g 1,2-propylene glycol 0.15 g perfume

0.5 g cetyltrimethylammonium chloride 45 g water ad 100 g ethanol

Example 8: Pump Spray Lotion

2 g macromer M2

0.2 g polyquaternium-16

0.4 g chitosan

2.5 g PVP / VA copolymer

0.12 g formic acid

0.15 g cetrimonium phosphate

0.1 g Laureth-4

0.1 g of 2-hydroxy-4-methoxybenzophenone

0.1 g perfume

50 g ethanol

Ad 100 g water

Example 9: Aerosol foam

2 g Macromer M3

2.00 g Polyquaternium-11 (Gafquat ^® 755) 0.45 g glyceryl laurate 0.15 g Perfume

0.16 g cetyltrimethylammonium chloride 5.00 g propane / butane (5.0 bar) 15 g ethanol ad 100 g water

Example 10: Aerosol foam 2 g macromer M4

3 40 g vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate terpolymer

0 60 g formic acid

0 60 g hydrogenated castor oil, ethoxylated with 40 mol

Ethylene oxide or 22 g of decyl polyglucoside

0.09 g cetyltrimethylammonium chloride o.20 g perfume

6.00 g propane / butane (5.0 bar)

Ad 100 g water

Example 11: Aerosol spray

Example 12: Pump spray

Example 13: Aerosol color foam

g Macromer M5

1.00 g polyquaternium-11 (Luviquat ^® PQ 11)

0.11 g of 3- (((2-nitro-4- (trifluoromethyl) phenyl) amino) -1,2-propanediol

0.20 g 1,2 propylene glycol

0.17 g perfume

0.10 g cetyltrimethylammonium chloride

6.00 g propane / butane (5.0 bar)

18.66 g ethanol

100 g water

Example 14: Color foam fixer 2 g macromer Ml

1.00 g polyquaternium-11 (Gafquat ^® 755)

20.10 g Colorona Carmine Red

0.20 g 1,2 propylene glycol

0.17 g of perfume

0.10 g cetyltrimethylammonium chloride

6.00 g propane / butane (5.0 bar)

18.66 g ethanol

Ad 100 g water

Example 15: Pump foam fixer

Example 16: Aerosol foam

In Examples 7-16, the macromer used in each case can be exchanged in whole or in part for one of the other macromers Ml to M17 or one or more of the shape memory polymers P1 to P8 listed below can be added with similar results.

Examples 17-26: Hair treatment with thermoplastic shape memory polymer

The shape memory polymers used in the following cosmetic products are produced from two different macrodiols and trimethylhexane-1,6-diisocyanate analogously to Example 1 of WO 99/42147.

The abbreviations of the macrodiols mean: PDX: polytpara-dioxanone) PLGA: poly (L-lactide-co-glycolide) PCL: poly (ε-caprolactone) PDL: poly (pentadecalactone)

The numbers given in the names of the macrodiols each represent the approximate molecular weight of the macrodiols (± 100).

The following hair treatment agents are used as follows: A sufficient amount of the agent is applied to the hair, depending on the length of the hair. The hair is brought into the desired shape, e.g. wrapped or stretched on winder and dried. The mixture is then heated to approximately 95 ° C. After cooling to room temperature (about 25 ° C), the winders are removed.

To emboss a second hairstyle shape (temporary shape), the first hairstyle shape is heated to approx. 55 ° C, brought into a second hairstyle shape and cooled to room temperature. When heated to approx. 55 ° C again, the first hairstyle spontaneously regresses.

Example 17: Hair fixative

0.5 g polymer pl

1.50 g vinyl pyrrolidone / vinyl acetate copolymer

0.20 g 1,2 propylene glycol

0.15 g perfume 0.5 g cetyltrimethylammonium chloride 45 g water ad 100 g ethanol

Example 18: Pump Spray Lotion

1 g of polymer P2

0.2 g polyquaternium-16

0.4 g chitosan

2.5 g PVP / VA copolymer

0.12 g formic acid

0.15 g cetrimonium phosphate

0.1 g Laureth-4

0.1 g of 2-hydroxy-4-methoxybenzophenone

0.1 g perfume

50 g ethanol

Ad 100 g water

Example 19: Aerosol foam

1.5 g polymer P3

2.00 g polyquaternium-11 (Gafquat ^® 755)

0.45 g glyceryl laurate

0.15 g perfume

0.16 g cetyltrimethylammonium chloride

5.00 g propane / butane (5.0 bar)

15 g ethanol

Ad 100 g water

Example 20: Aerosol foam

2 g polymer P4

3.40 g vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate terpolymer 0.60 g formic acid 0.60 g hydrogenated castor oil, ethoxylated with 40 mol

ethylene oxide

0.22 g decyl polyglucoside

0.09 g cetyl trimethyl ammonium chloride

0.20 g perfume

6.00 g propane / butane (5.0 bar)

Ad 100 g water

Example 21: Aerosol spray

Example 22: Pump spray

Example 23: Aerosol color foam

0.5 g polymer P7

1.00 g polyquaternium-11 (Luviquat ^® PQ 11)

0.11 g of 3- (((2-nitro-4- (trifluoromethyl) phenyl) amino) -1, 2-propanediol 0.20 g of 1,2-propylene glycol 0.17 g perfume

0.10 g cetyltrimethylammonium chloride

6.00 g propane / butane (5.0 bar)

18.66 g ethanol

Ad 100 g water

Example 24: Color foam fixer

1 g of polymer P8

1.00 g polyquaternium-11 (Gafquat ^® 755)

20.10 g Colorona Carmine Red

0.20 g 1,2 propylene glycol

0.17 g perfume

0.10 g cetyltrimethylammonium chloride

6.00 g propane / butane (5.0 bar)

18.66 g ethanol

Ad 100 g water

Example 25: Pump foam fixer

Example 26: Aerosol foam

In Examples 17 to 26, the shape memory polymer used in each case can be exchanged in whole or in part for one of the other polymers P1 to P8 with similar results.

Claims

claims

1. A method of hair treatment, wherein

an active substance composition is applied to the hair, the active substance composition containing at least a first active substance or first active substance complex, which are selected or formed from substances which, alone or in combination with further substances, are capable of being applied to hair and after Carrying out the treatment described below to give the hair a shape memory effect, and the active ingredient composition contains at least one second active ingredient which is selected from cationic active ingredients, - before, at the same time or after the application of the active ingredient composition, the hair in a specific shape (permanent Memory form) is brought and then the memory form is fixed by inducing a chemical or physical change in the applied active ingredients; wherein after an intentional or unwanted deformation of the shape of the memory, the original shape of the memory can essentially be restored by physical stimulation.

2. The method according to claim 1, characterized in that the active substance composition contains at least two active substances which individually have no or only weak ones

Have shape memory properties and, when used together in accordance with the method of claim 1, give hair a synergistically increased shape memory effect.

3. The method of claim 1, wherein - The first active ingredient is a crosslinkable macromer, which forms a shape memory polymer after crosslinking, the macromer containing a) crosslinkable areas that can be crosslinked by chemical bonds and b) thermoplastic areas that are not chemically crosslinkable, - the shape of memory by chemical crosslinking of the macromer is fixed to form the shape memory polymer, and wherein the shape memory polymer has at least one transition temperature Ttrans.

4. A method for hair treatment, wherein - one programmed by a method according to claim 3

Hairstyle (permanent shape) is heated to a temperature above Ttrans, the hair is brought into a second (temporary) shape and the second shape is fixed by cooling to a temperature below Ttrans.

5. The method according to claim 3 or 4, characterized in that the crosslinkable macromer is selected from compounds of the general formula Al- (X) _n -A2 where AI and A2 are reactive, chemically crosslinkable groups and - (X) n- for is a divalent, thermoplastic polymer or oligomer segment.

6. The method according to claim 5, characterized in that the crosslinkable macromer is selected from polyesters, oligoesters, polyalkylene glycols, oligoalkylene glycols, polyalkylene carbonates and oligoalkylene carbonates substituted with at least two acrylate or methacrylate groups.

7. The method according to claim 6, characterized in that the crosslinkable macromer is selected from poly (ε-caprolactone) dimethacrylate, poly (DL-lactide) dimethacrylate, poly (L-lactide-co-glycolide) dimethacrylate, poly ( ethylene glycol) dimethacrylate, poly (propylene glycol) dimethacrylate, PEG-block-PPG-block-PEG-dimethacrylate, poly (ethylene adipate) dimethacrylate, hexamethylene carbonate dimethacrylate.

8. The method according to any one of the preceding claims, characterized in that the composition additionally contains a macromer with only one terminal or pendant, chemically reactive group.

9. The method of claim 1, wherein

- The first active ingredient is a shape memory polymer which a) at least one hard segment that can be crosslinked by physical interaction with a first transition temperature T 'trans which is above room temperature, and b) at least one soft segment with a second one

Transition temperature trans, which is below T ¹ trans, and

- The shape of the memory is fixed by physical networking of the shape memory polymers.

10. The method according to claim 9, characterized in that the

Shaping of the hair takes place with heating to a temperature of at least T 'trans and that the subsequent fixing of the hair shape takes place by cooling to a temperature below T' trans.

11. Method for hair treatment, wherein a hairstyle (permanent shape) programmed by a method according to claim 9 or 10 is heated to a temperature between T ¹ trans ^{un (} d Tt ans), the hair is brought into a second (temporary) shape and - the second shape is cooled to one Temperature below Ttrans is fixed.

12. A method for reprogramming a hairstyle (permanent shape) previously programmed by a method according to claim 9 into a new permanent shape, wherein

- The hairstyle is heated to a temperature above T 'trans

- is brought into a new form and

- The new shape is then fixed by cooling to a temperature below T 'trans.

13. The method according to any one of claims 9 to 12, characterized in that the shape memory polymer has a degree of crystallinity of 3 to 80% and that the ratio of the elastic modulus below and above Ttrans is at least 20.

14. The method according to any one of claims 9 to 13, characterized in that the shape memory polymer is a copolyester urethane.

15. The method according to claim 14, characterized in that the

Shape memory polymer, the reaction product of (a) two different macrodiols, selected from α, ω-dihydroxy polyesters, α, ω-dihydroxy-oligoesters, α, ω-dihydroxy-polylactones and α, ω-dihydroxy-oligolactones and (b) at least one Is diisocyanate.

16. Procedure to restore a previously through one

The method of claim 1, 3, 9 or 12 programmed hairstyle (permanent shape), wherein a hairstyle in a temporary shape according to claim 4 or claim 11 or a cold-deformed hairstyle is heated to a temperature above Ttrans.

17. The method according to any one of the preceding claims, characterized in that the cationic, second active ingredient is selected from surfactants with cationic or cationizable groups, polymers with cationic or cationizable groups, silicone compounds with cationic or cationizable groups, cationically derivatized proteins, cationically derivatized protein hydrolyzates and betaine.

18. The method according to claim 17, characterized in that the cationic surfactant is selected from compounds of the general formula

_N ( ₊ ) _R 1 _R 2 _R 3 _R 4 _χ (-) where Rl to R4 independently of one another denote aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 carbon atoms, where the Alkyl groups can be linear, branched or cyclic and where at least one of the groups has at least 8 carbon atoms and X ~ represents an anion.

19. The method according to claim 17, characterized in that the cationic polymer is selected from methylvinyl imidazolium chloride / vinyl pyrrolidone copolymers, quaternized vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymers, dimethyl diallyl ammonium chloride / sodium acrylate / acrylamide copolymers, vinyl pyrrolidone / dimethylaminoethylrolactamate / copolymer vinylpyrrolidone / methacrylamidopropyltrimethylammonium Copolymer, cationically derivatized polysaccharides, chitosan, chitosan salts, chitosan derivatives.

20. The method according to any one of the preceding claims, characterized in that the active ingredient composition contains the first active ingredient in an amount of 0.01 to 25% by weight and the second active ingredient in an amount of 0.01 to 25% by weight.

21. Hair cosmetic composition containing an active ingredient complex in a suitable cosmetic base, the active ingredient complex containing at least a first active ingredient, which is selected from substances which, alone or in combination with other substances, are capable of being applied to hair and after having been carried out Method according to one of claims 1 to 20 to give the hair a shape memory effect, and wherein the active ingredient complex contains at least one second active ingredient which is selected from cationic active ingredients.

22. The composition according to claim 21, characterized in that the first active ingredient is either one to one

Shape memory polymer is crosslinkable macromer, wherein the crosslinked shape memory polymer has at least one transition temperature Ttrans and wherein the macromer a) contains crosslinkable regions which can be separated by chemical

Bonds are crosslinkable and b) contains thermoplastic areas that are not chemically crosslinkable; and / or that the first active ingredient is a shape memory polymer which a) has at least one hard segment which can be crosslinked by physical interaction with a first Transition temperature T ¹ trans, which is above room temperature, and b) at least one soft segment with a second

Transition temperature Ttrans, which is below T ¹ trans; and the second active ingredient is selected from surfactants with cationic or cationizable groups, polymers with cationic or cationizable groups,

Silicone compounds with cationic or cationizable groups, cationically derivatized proteins, cationically derivatized protein hydrolyzates and betaine.

23. The composition according to claim 22, characterized in that the cationic surfactant is selected from compounds of the general formula

_N ( ₊ ) _R 1 _R 2 _R 3 _R 4 _χ (-) where Rl to R4 independently of one another denote aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 carbon atoms, where the

Alkyl groups can be linear, branched or cyclic and where at least one of the groups has at least 8 carbon atoms and X ^"represents an anion.

24. The composition according to claim 22, characterized in that the polymer with cationic or cationizable groups is selected from methylvinylimidazolium chloride / vinylpyrrolidone copolymers, quaternized vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers, cationically derivatized polysaccharides, chitosan, chitosan salts, chitosan derivatives.

25. The composition according to any one of claims 21 to 24, characterized in that the shape memory polymer is 0.01 to 25 % By weight and the cationic active ingredient in an amount of 0.01 to 25% by weight.

26. The composition according to any one of claims 21 to 25, characterized in that at least two active ingredients are contained, which individually have no or only weak

Have shape memory properties and, when used together according to the method of claim 1, give hair a synergistically increased shape memory effect.

27. Cosmetic composition containing a composition according to any one of claims 21 to 26, characterized in that it is in the form of a lotion, a spray lotion, a cream, a gel, a gel foam, an aerosol spray, a non-aerosol spray, an aerosol foam, a non Aerosol foam, an O / W or W / O emulsion, a microemulsion or a hair wax.

28. Composition according to claim 27, characterized in that it additionally contains 0.01 to 25% by weight of at least one active substance, selected from hair-care substances, hair-setting substances and hair-coloring substances.