EP1492494A1 - Method for treating hair with form memory polymers - Google Patents

Method for treating hair with form memory polymers

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Publication number
EP1492494A1
EP1492494A1 EP20030724998 EP03724998A EP1492494A1 EP 1492494 A1 EP1492494 A1 EP 1492494A1 EP 20030724998 EP20030724998 EP 20030724998 EP 03724998 A EP03724998 A EP 03724998A EP 1492494 A1 EP1492494 A1 EP 1492494A1
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EP
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Application
Patent type
Prior art keywords
hair
macromer
amino
poly
shape
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20030724998
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German (de)
French (fr)
Inventor
Jürgen Allwohn
Johannes Burghaus
Werner Grasser
Axel Kalbfleisch
Karl Kratz
Thomas Krause
Günther LANG
Andreas Lendlein
Detlef Mattinger
Gerhard Sendelbach
Stefan Uhl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MnemoScience GmbH
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MnemoScience GmbH
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Publication date

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/416Quaternary ammonium compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/594Mixtures of polymers

Abstract

A method for achieving a reproducible hair shaping using form memory polymers is disclosed. A composition comprising a macromer or pre-polymer which may be cross-linked to give a form memory polymer is applied to the hair, the hair is shaped in a particular (permanent) form and the permanent form fixed by means of chemical cross-linking of the macromer or pre-polymer to generate a form memory polymer. The macromers or pre-polymers comprise regions which may be cross-linked by means of chemical bonds and non-chemically cross-linkable thermoplastic regions. The form memory polymers have at least one transition temperature Ttrans. In addition to the permanent hair style a second (temporary) style can also be generated. Furthermore a method is disclosed for the reproduction of a previously programmed permanent hair style which has been transiently transformed into a temporary form or otherwise misshapen.

Description

Method of treating hair with shape memory polymers

The present invention is a method for obtaining a retrievable hair shaping using shape memory polymers.

In the shaping of hair hair shaping distinction is generally between temporary and permanent, permanent. A temporary hair shaping is generally carried out using compositions based on solutions or dispersions hair-setting polymers. Such products give the hair by the addition of polymer more or less hold, volume, elasticity, bounce and shine. These styling products facilitate, for example, as a gel shaping and creating the hairstyle, better than hairspray increase the level of a hairstyle created and as Festigerschaum the volume of hair. A disadvantage is that the desired effects only of relatively short duration and will be lost due to external influences such as combing, wind, high humidity and contact with water quickly. A permanent hair shaping is usually done by a permanent wave treatment. Here disulfide bonds are reductively cleaved in the hair, put the hair in the new form and fixed by oxidative formation of new disulfide bonds. The disadvantage is that due to the required chemical treatment of the hair with a reducing and oxidizing agents

Damage to the hair structure can not be avoided. Another disadvantage of the previously known methods for hair forming, it is not possible to make a transformation in a relatively simple manner reversed, ie to move from one hairstyle without extensive rebuilding to another.

From JP 04-41416 hair cosmetics are known which contain certain linear polyurethanes having a glass transition temperature Tg of 40 90 ° C. The described method for hair treatment corresponds to a treatment with a typical thermoplastics. After applying the composition, the hairstyle is created and fixed by cooling below Tg above Tg. Upon renewed heating above Tg the polymer softens and a new hairstyle can be created. A method for a retrievable, reversible hair forming is not described. The properties of linear polyurethanes are insufficient for an application for retrievable hair restyling.

The the present object underlying the invention was to provide a process and the necessary products for a retrievable hair styling with a high degree of recovery of a programmed hairstyle form. Another object was to make available a process with which it is possible to achieve permanent hair restyling without damaging intervention in the hair structure. Another object was to make available a process which allows to make temporary transformations multiply easily reversed and started with high accuracy to a previously programmed permanent hairstyle. Another object was to make available a process which allows to make due in a simple manner and with high accuracy to external influences deformations of a hairstyle reversed and started to a previously programmed permanent hairstyle.

The object is achieved by a method for hair treatment, wherein - a composition comprising at least one crosslinkable

Macromer which forms after curing a shape memory polymer is applied to the hair, wherein the macromer a) contains cross-linkable regions that are cross-linkable through chemical bonds and b) contain thermoplastic regions that are not chemically crosslinked, before, simultaneously or subsequently the hair subsequently, the mold by chemical crosslinking of the macromer to form the shape memory polymer is fixed, wherein the shape memory polymer comprises at least one transition temperature T trans - in a specific (permanent) shape and lacked .If.

Another object of the invention is a method for

Impressing a second hair style over a programmed, retrievable first hairstyle. In this case, a programmed by the above method hairstyle (permanent shape) is first heated to a temperature above T trans. The hair is then placed in the desired second form (temporary) and the second shape is fixed by cooling to a temperature below T trans.

Another object of the invention is a process for the recovery of a previously programmed by the above method first hairstyle (permanent shape). For this purpose, a hairstyle in a temporary shape or a deformed by cold deformation of hair is heated to a temperature above T trans.

Shape memory polymers in accordance with the invention are polymers from which materials can be produced with the property that makes them any shape (permanent shape) impart, after a deformation or after impressing a second mold (temporary shape) in which it spontaneously and without outer

reconvert force by simple heating or by other energetic stimulus. Deformation and reconversion (recovery) are multiple possible. The degree of achievement of the original, permanent shape is somewhat lower than in subsequent cycles in a first relaxation cycle consisting of deformation and reconversion, usually, defects, textures etc .. A particularly high probably due to the elimination of initially still present. is degree of recovery but then in the subsequent

Relaxation cycles achieved. The degree of recovery is in the first relaxation preferably at least 30%, more preferably at least 50% and in the subsequent relaxation is preferably at least 60%, particularly preferably at least 80%. but it may also be 90% or more. The degree of recovery can be measured as in the conventional curl retention measurements by simple length of a treated hair tress, or by known suitable train-strain experiments.

To shape memory polymers crosslinkable macromers or prepolymers according to the invention are polymers or oligomers in which the fixing of an impressed permanent shape is achieved in that individual polymer or oligomer strands are linked together by chemical bonds. The cross-linking chemical bonds can be made via ionic or covalent bonds. The crosslinking reaction can be any chemical reaction, such as a salt-forming reaction, a condensation reaction, an addition reaction, a substitution reaction or a radically or photochemically induced reaction. The crosslinking reaction can be carried out by means of suitable initiators or catalysts or catalyst-free. It can be triggered by a suitable power source, for example by electromagnetic radiation, ultrasound, heat or mechanical energy. A combination of two or more methods may optionally be used to increase the efficiency or speed of the crosslinking reaction.

According to the invention suitable shape memory polymers have at least one transition temperature T trans. This may 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- The ratio of the moduli of elasticity below and above T trans i st preferably at least 20. Preferably, the transition temperature Ttrans i st greater than room temperature (20 ° C), especially at least 30 ° C, more preferably at least 40 ° C and is the temperature above which the spontaneous recovery of the permanent shape from the deformed or from the temporary mold.

Hairstyle or hairstyle according to the invention has a broad meaning and comprises, for example, the degree of curl or the degree of smoothness of hair. A programmed hairstyle according to the invention is a collection of hair, by the fixed cross-linked and in the form of a permanent

Shape memory polymers having a certain shape. Restoring a programmed hairstyle in the sense of the invention means that the programmed hairstyle after deformation again preferably at least 60%, particularly preferably regresses at least 80%, based on the shape which results after a first relaxation. The degree of recovery can be effected for example by length measurement of a lock of hair or a hair strand.

Suitable to shape memory polymers chemically cross-linkable

Macromers or prepolymers are macromonomers that can be polymerized or crosslinked by individual chemical bonds. The chemically cross-linked polymers are referred to in WO 99/42147 as Thermosetpolymere. The macromers and Thermosetpolymere described in WO 99/42147 are suitable for the invention and part of this application. Soft, thermoplastic segments (switching segments) with a transition temperature T trans are crosslinked by chemical, preferably covalent bonds. It requires switching segments and network points, the network points determine the permanent shape and switching segments, the temporary shape. The shape memory effect is based on the change in the elasticity at above or below the lower Ttrans- The ratio of the elasticity modules and preferably above Ttrans i st at least 20. The higher this ratio, the more pronounced is the shape memory effect. There can be four types of thermoset polymers differ with shape memory properties: network polymers, interpenetrating networks, semi-interpenetrating networks and mixed interpenetrating networks. Network polymers can be formed by covalent linkage of Macro mono older, ie, of oligomers or polymers having linkable reactive end groups, preferably ethylenically unsaturated, free-radically or photochemically reactive end groups. The crosslinking reaction may for example be initiated by light or heat sensitive initiators, by redox systems or combinations thereof or initiator free, for example by UV light, heat or mechanical energy. Pervasive networks are formed of at least two components each are not linked to each other but for themselves. Mixed-interpenetrating networks are formed from at least two components, wherein one component by chemical bonds and another component is cross-linked by physical interactions. Semi-interpenetrating networks are formed from at least two components, one of which is chemically cross-linkable and the other is not crosslinkable and both components can not be separated by physical methods.

Basically suitable are all synthetic or natural oligomers and polymers having reactive end or side groups including a suitable transition temperature Ttrans unc ^ above suitable elasticity modules the crosslinked From memory polymer and impart below Ttrans and wherein the end or side groups either during manufacture or subsequently, by derivatization present in a reactive form, which allow a crosslinking reaction with the above mentioned methods. Suitable macromers are those of the general formula Al (X) n -A2 (I) wherein Al and A2 represent reactive, chemically cross-linkable groups and - (X) n- represents a divalent, thermoplastic polymer or oligomer. Al and A2 are preferably acrylate or methacrylate groups. The segment (X) n is preferably polyester, oligoester, polyalkylene glycol, Oligoalkylenglykol-, Polyalkylencarbonat- and Oligoalkylencarbonatsegmente, wherein the alkylene groups, preferably ethylene or propylene groups. Suitable macromonomers to form thermoset polymers with shape memory properties are oligo- or poly (ε-caprolactone), oligo- or polylactides, oligo- or polyalkylene glycols, for example,

Polyethylene or polypropylene glycol or block copolymers thereof, wherein the polymers or oligomers of said terminal or pendant free-radically polymerizable with at least two ethylenically unsaturated groups, such as acrylates or methacrylates are substituted.

The polymer segments, it may be derived from natural polymers such as proteins or polysaccharides segments. It can also be synthetic polymer blocks themselves. Suitable natural polymer segments are proteins such as zein, modified zein, casein, gelatin, gluten, serum albumin, or collagen, and polysaccharides such as alginates, celluloses, dextran, pullulan or polyhyaluronic acid, as well as chitin, poly (3-hydroxyalkanoate), especially poly (.beta. hydroxybutyrate), poly (3- hydroxyoctanoates) or poly (3-hydroxyfatty acids). Also suitable are derivatives of natural polymer segments, for example, alkylated, hydroxyalkylated, hydroxylated or oxidized modifications. Synthetically modified natural Polmere are for example cellulose derivatives loseether as alkylcelluloses, hydroxyalkylcelluloses, cellulose ethers, cellulose esters, nitro celluloses, chitosan or chitosan derivatives, for example, by N- and / or O-alkyl or hydroxyalkyl substitution are obtained. Examples are methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, cellulose acetate phthalate, carboxymethyl cellulose, cellulose triacetate or cellulose sulfate sodium salt. These are referred to below as "celluloses".

Suitable synthetic polymer blocks are polyphosphazenes, poly (vinyl alcohols), polyamides, polyesteramides, polyaminoacids, polyanhydrides, polycarbonates, polyacrylates, polyalkylenes, polyacrylamides, polyalkylene glycols, Polyalkylenσxide, polyalkylene terephthalates, polyortho esters, polyvinyl ethers, polyvinyl esters, polyvinyl halides, polyvinylpyrrolidone, polyesters, polylactides, polyglycolides, polysiloxanes , polyurethanes and copolymers thereof. Examples of suitable polyacrylates include poly (rαethylmethacrylat), 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 synthethische, easily biodegradable polymer segments are polyhydroxy acids such as polylactides, polyglycolides and copolymers thereof, poly (ethylene terephthalate); Poly (hydroxybutyric acid); Poly (hydroxyvaleric acid); Poly [lactide-co- (ε-caprolactone)]; Poly [glycolide-co- (ε-caprolactone)]; Polycarbonates, poly (amino acids); Poly (hydroxyalkanoates); polyanhydrides; Polyorthoesters as well as their mixtures and copolymers. Examples of poor biodegradable polymer segments are poly (methacrylic acid), poly (acrylic acid), polyamides, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylphenol, and copolymers and mixtures thereof.

Compositions of the invention for. the hair treatment contain at least one of the above, to

Shape memory polymers crosslinkable macromers or prepolymers in an amount of preferably 0.01 to 25.%, Particularly preferably from 0.1 to 15.% In a suitable liquid medium. The composition may be a solution, dispersion, emulsion, suspension, or latex. The liquid medium is preferably cosmetically acceptable and physiologically harmless.

In a particularly preferred embodiment, the composition comprises 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 those of the general formula

R- (X ') n -A3 (II) where R is a monovalent organic residue, A3 designates a reactive, chemically cross-linkable group and - (X' stands) n designates a divalent, thermoplastic polymer or oligomer. A3 is preferably an acrylate or methacrylate. The segment (X ') n preferably stands for the polyalkylene glycols, the monoalkyl ethers and block copolymers thereof, wherein the

Alkylene, preferably ethylene or propylene groups, and the alkyl groups preferably have 1 to 30 carbon atoms. Particularly preferred are mixtures of (A) terminally at both ends with acrylic or methacrylic acid esterified polyalkylene glycols or polycaprolactones and (B) terminal at one end with acrylic or methacrylic acid esterified polyalkylene glycol monoalkyl ethers, wherein the alkylene groups are preferably ethylene or propylene groups and the alkyl groups preferably Cl- are to C30 alkyl groups. As component (A) are for example suitable: 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-PEG block-dimethacrylate, poly (ethylene adipate) dimethacrylate, hexamethylene dimethacrylate. As the component (B) are for example suitable: poly (ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate, and their monoalkyl ethers.

The composition of the invention is generally a solution or dispersion in a suitable solvent. Especially preferred aqueous, alcoholic or aqueous-alcoholic solvents. Suitable solvents are aliphatic Cl-C4 alcohols or a mixture of water with one of these alcohols. However, other organic

Solvents are used, in particular, linear 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 such as ethyl acetate may be mentioned. Further, suitable solvents are silicone based, especially silicone oils based on linear or cyclic polydimethylsiloxanes (Dimethicone or Cyclomethicone). The solvents are preferably present in an amount of 0.5 to 99 wt.%, Particularly preferably in an amount of 40 to 90.% Before.

Compositions of the invention may additionally 0.01 to 25 wt.% Containing at least one hair-care, hair-setting and / or hair-coloring agent.

Hair setting agents are in particular the known conventional film-forming and hair-setting polymers. The film-forming and hair-fixing polymer can be synthetic or natural origin and nonionic, cationic, anionic or amphoteric have character. Such a polymeric additive is present in amounts of 0.01 to 25th%, preferably 0.1 to 20th%, particularly preferably from 0.5 to 15 °.% May be contained, may also consist of a mixture of several Polymerern exist and are modified by the addition of other polymers with a thickening effect in its hair-setting properties. Film-forming, hair-setting polymers, such polymers are understood according to the invention, the aqueous, alcoholic or aqueous-alcoholic solution, are able on the hair when used in a 0.01 to 5%

deposit polymer film and consolidating in this way the hair.

Suitable synthetic, nonionic film-forming, hair-fixing polymers may be used in the inventive hair treatment agent, homopolymers of vinyl pyrrolidone, homopolymers of N-vinylformamide, Copol merisate of vinylpyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides, polyvinyl alcohols, or polyethylene glycols having a molecular weight of 800 to 20,000 g / mol. Among the suitable synthetic film-forming anionic polymers are crotonic acid / vinyl acetate copolymers and terpolymers of acrylic acid, ethyl acrylate and Nt-butylacrylamide. Natural film-forming polymers or polymers produced therefrom by chemical conversion may also be employed in the inventive hair treatment compositions. is low molecular weight chitosan have proven having a molecular weight from 30,000 to 70,000 g / mol or high molecular weight chitosan, derivatives of chitosan organolösliehe, mixtures of oligo-, mono- and disaccharides, Chinese balsam resin, cellulose derivatives such as

Hydroxypropyl cellulose having a molecular weight of 30,000 to 50,000 g / mol, or shellac in neutralized or unneutralized form. Amphoteric polymers may also be used in the inventive hair treatment agents. Suitable z. For example, copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers from the group of acrylic acid, methacrylic acid and simple esters thereof. Among the cationic polymers that can be used in this invention are copolymers of vinyl pyrrolidone with quaternized derivatives of Dialkylaminoacrylats- and - methacrylate such as, to name, for example, quaternized with diethyl sulfate vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers. Other cationic polymers include the copolymer of vinyl pyrrolidone with vinyl, the

Terpolymer of dimethyl diallyl ammonium chloride, sodium acrylate and acrylamide, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and Vinylcarprolactam, the quaternized ammonium salt prepared from hydroxyethyl cellulose and a trimethylammonium-substituted epoxide, the vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer and diquaternary polydimethylsiloxanes.

The consistency of the hair treatment composition of the invention can be increased by adding thickeners. For this purpose, for example, 'homopolymers of acrylic acid are suitable with a molecular weight from 2 million to 6 million g / mol. Copolymers of acrylic acid and acrylamide (sodium salt) having a molecular weight from 2 million to 6 million g / mol, Sclerotium gum and copolymers of acrylic acid and methacrylic acid are suitable.

An inventive cosmetic composition can be applied in various application forms, such as in the form of a lotion, a spray lotion, a cream, a gel, a Gelschaums, an aerosol spray, a Nonaerosolsprays, an aerosol foam, a Nonaerosolschaums, an O / W or W / 0- emulsion, a microemulsion or a hair wax. When the hair treatment composition of the invention is in the form of an aerosol spray it additionally contains 15 to 85 wt.%, Preferably 25 to 75 wt.% Of a propellant and is bottled in a pressurized container with a spray head. As a blowing agent, lower alkanes, such as n-butane, isobutane and propane, or also their mixtures as well as dimethyl ether or fluorohydrocarbons such as F 152a (1, 1-difluoroethane) or F 134 (tetrafluoroethane) as well as also at the pressures in question in gaseous form such as N 2, O 2 and CO 2 and mixtures of the aforementioned propellants suitable propellant.

When the hair treatment composition of the invention is in the form of a sprayable non-aerosol hair spray, it is sprayed with the help of a suitable mechanically operated spraying device. Mechanical spraying devices are understood which allow the spraying of a composition without use of a propellant. A suitable mechanical spraying device can for example be a spray pump or in the cosmetic composition of the invention is bottled under pressure provided with a spray elastic container, wherein the elastic container expands and from which the composition continuously due to the contraction of the elastic container on opening the spray valve are emitted used.

When the hair treatment composition of the invention is in the form of a hair foam (mousse), it contains at least one customary foam-imparting substance known for this purpose. The composition is foamed with or without the aid of propellant gases or chemical propellants and worked into the hair as foam and without

Rinse left in the hair. A product of the invention comprises a device for foaming the composition as an additional component. Devices for foaming are understood to be those devices which enable the foaming of a liquid with or without use of a propellant. A suitable mechanical foaming device, for example, a commercially available foam pump or an aerosol foam head can be used.

When the hair treatment composition of 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, more preferably from 0.1 to 2 wt.%. The viscosity of the gel is preferably from 100 to 50,000mm / s, more preferably from 1, 000 to 15,000 mm 2 / s at 25 ° C, measured as dynamic viscosity using a Bohlin rheometer CS, measurement body C25 at a shear rate of 50 s ~.

When the hair treatment composition of the invention in the form of a

Hair wax is present, it additionally contains water-insoluble fatty or achsstoffe or substances which impart a wax-like consistency of the composition, is present in an amount of preferably 0.5 to 30.%. Suitable water-insoluble substances are, for example E ulgatoren having 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 having a molecular weight of 800 to 20,000, preferably from 2,000 to 10,000 g / mol.

When the hair treatment composition of the invention is in the form of a hair lotion, it is present as a non-viscous or low-viscous, flowable essentially solution, dispersion or emulsion with a content of at least 10 wt.%, Preferably 20 to 95 wt.% Of a cosmetically compatible alcohol in front. As alcohols, particularly the lower Cl commonly used for cosmetic purposes can be used to C4 alcohols such as ethanol and isopropanol.

When the hair treatment composition of the invention is in the form of a hair cream, it is preferably present as an emulsion and comprises either additionally iskositätsgebende ingredients in an amount of 0.1 to 10 wt.% Or the required viscosity and creamy consistency is built up through micelle formation with the aid of suitable emulsifiers , fatty acids, fatty alcohols, waxes, etc. constructed in the usual manner.

In a preferred embodiment, the inventive composition capable of gleizeitig to allow both the impressing a retrievable hair and a hair dyeing. The agent is then formulated as a coloring hair treatment agent such as a dye fixatives, dye cream, etc. coloring foam. It then comprises at least one f rbenden fabric. These may be organic dyes, in particular so-called direktziehnde dyes or also inorganic pigments.

The total amount of Farbstof s is in the inventive composition is about 0.01 to 7 wt.%, Preferably about 0.2 to 4 wt.%. aromatic nitro dyes, azo dyes, quinone dyes, cationic or anionic dyes, for example triphenylmethane dyes for the agents of the invention suitable direct dyes. These are: nitro dyes (blue):

1,4-bis [(2-hydroxyethyl) amino] -2-nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene (HC Blue No . 2), l-amino-3-methyl-4- [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 4- [ethyl- (2-hydroxyethyl) amino] -l- [ (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 12), 4- [di (2-hydroxyethyl) amino] -1- [(2-methoxyethyl) amino] -2-nitrobenzene (HC Blue No. 11), 1- [(2,3-dihydroxypropyl) amino] -4- [methyl- (2-hydroxyethyl) amino] -2-nitrobenzene (HC Blue No. 10), 1- [(2, 3- dihydroxypropyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Blue No. 9), 1- (3-hydroxy-propylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzene (HC Violet No. 2), l-methylamino-4- [methyl- (2, 3-dihydroxypropyl) amino] -2-nitrobenzene (HC Blue No. 6), 2- (4- ( amino-2-nitrophenyl) amino) -5- dimethylamino-benzoic acid (HC Blue No. 13), 1- (2-aminoethylamino) - 4- [di (hydroxyethyl) amino] -2-nitrobenzene, 4- (di ( 2 hydroxyethyl) amino) -2-nitro-l-phenylamino-benzene.

Nitro dyes (red): l-amino-4- [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 7), 2-amino-4, 6-dinitro-phenol, 1, 4-diamino-2 nitrobenzene (CI76070), 4-amino-2-nitro-diphenylamine (HC Red No. 1), 1-amino-4- [di (2-hydroxyethyl) amino] -2-nitrobenzene hydrochloride (HC Red No. 13 ), 1-amino-5-chloro-4- [(2-hydroxyethyl) amino] -2-nitrobenzene, 4-amino-1- [(2-hydroxyethyl) amino] -2-nitrobenzene (HC REDNO. 3), 4- ((2-hydroxyethyl) methylamino) -1- (methylamino) -2-nitrobenzene, 1-amino-4- ((2,3-dihydroxypropyl) amino) -5-methyl-2-nitrobenzene, l-amino 4- (methylamino) -2-nitrobenzene, 4-amino-2-nitro-l- ((prop-2-en-l-yl) - amino) -benzene, 4-amino-3-nitrophenol, 4- [( 2-hydroxyethyl) amino] -3-nitrophenol, 4- [(2-nitrophenyl) amino] phenol (HC Orange No. 1), 1- [(2-aminoethyl) amino] -4- (2-hydroxyethoxy) -2 nitrobenzene (HC Orange No. 2), 4- (2,3-dihydroxypropoxy) -1- [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Orange No. 3), l-amino-5-chloro- 4- [(2, 3- dihydroxypropyl) on ino] -2-nitrobenzene (HC Red No. 10) 5-chloro-l, 4- [di (2, 3-dihydroxypropyl) amino] -2-nitrobenzene (HC Red No. 11), 2- [(2-hydroxyethyl) amino] -4, 6-dinitro phenol, 4-ethylamino-3-nitrobenzoic acid, 2- [(4-amino-2-nitrophenyl) amino] benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4- nitro phenol, 4- [(3-hydroxypropyl) amino] -3-nitrophenol, 2,5-diamino-6-nitropyridine, 6-amino-3- ((2-hydroxyethyl) amino) -2-nitropyridine, 3- amino-6- ((2-hydroxyethyl) amino) -2-nitropyridine, 3-amino-6- (ethylamino) -2-nitropyridine, 3- ((2-hydroxyethyl) amino) -6- (methylamino) -2- nitropyridine, 3-amino-6- (methylamino) -2-nitropyridine, 6- (ethylamino) -3- ((2-hydroxyethyl) amino) -2-nitropyridine, l, 2,3,4-tetrahydro-6-nitroquinoxaline , 7-amino-3,4-dihydro-6-nitro-2H-l, 4-benzoxazine (HC Red No. 14).

Nitro dyes (yellow):

1, 2-diamino-4-nitrobenzene (CI76020), l-amino-2- [(2-hydroxyethyl) amino] -5-nitrobenzene, 1- (2-hydroxyethoxy) (HC Yellow No. 5). - 2- [ (2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 4), l - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow No. 2), 2- (di (2-hydroxyethyl) amino) -5-nitro-phenol, 2- [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1-amino-2-methyl-6-nitrobenzene, 1- (2 hydroxyethoxy) -3-methylamino-4-nitrobenzene, 2,3- (dihydroxypropoxy) -3-methylamino-4-nitrobenzene, 2- [(2-hydroxyethyl) amino] -5-nitrophenol (HC Yellow No. 11), 3- [2- (

Aminoethyl) amino] -l-methoxy-4-nitrobenzene hydrochloride (HC Yellow No.9), 1- [(2-ureidoethyl) amino] -4-nitrobenzene, 4 - [(2,3-dihydroxypropyl) amino] - 3-nitro-l-trifluoromethyl-benzene (HC Yellow No. 6), l-chloro-2, 4-bis [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 10), l-amino 4- ((2-aminoethyl) amino) -5-methyl-2-nitrobenzene, 4- [(2-hydroxyethyl) amino] -3-nitro-l-methylbenzene, 1-chloro-4- [(2-hydroxyethyl) amino] -3 -nitrobenzene (HC Yellow No. 12), 4- [(2-hydroxyethyl) amino] -3-nitro-l-trifluoromethyl-benzene (HC Yellow No. 13), 4- [(2-hydroxyethyl) amino] -3-nitro-benzonitrile (HC Yellow No. 14), 4- [(2-hydroxyethyl) amino] -3-nitro-benzamide (HC

Yellow No. 15) 3- ((2-hydroxyethyl) amino) -4-methyl-l-nitrobenzene, 4-chloro-3- ((2-hydroxyethyl) amino) -1-nitrobenzene.

Quinone dyes: 1,4-di [(2, 3 -dihydroxypropyl) amino] -9, 10-anthraquinone, 1,4-di [(2- hydroxyethyl) amino] -9, 10-anthraquinone (CI61545, Disperse Blue 23) , 1- [(2-hydroxyethyl) amino] - -methyl-9, 10-anthraquinone (CI61505, Disperse Blue No. 3), 2- [(2-aminoethyl) amino] -9, 10-anthraquinone (HC Orange No . 5) l-amino-4-hydroxy-9, 10-anthraquinone (CI60710, Disperse Red 15), l-hydroxy-4- [(4-methyl-2-sulfophenyl) amino] -9 10-anthraquinone, 7-Beta-D-glucopyranosyl- 9,10-dihydro-l-methyl-9,10-dioxo-3,5, 6, 8-tetrahydroxy-2-anthracenecarboxylic acid (CI75470, Natural Red 4), 1- [(3 - aminopropyl) amino] -4-methylamino-9, 10-anthraquinone (HC Blue No. 8), 1- [(3-aminopropyl) amino] -9, 10-anthraquinone (HC Red No. 8), l, 4 diamino-2-methoxy-9,10-anthraquinone (CI62015, Disperse Red No. 11, Solvent Violet No. 26), 1-dihydroxy-5, 8-bis [(2-hydroxyethyl) amino] -9, 10 anthraquinone (CI62500, Disperse Blue No. 7, Solvent Blue No. 69), 1, 4-diamino-9, 10-anthraquinone (CI61100, D isperse Violet No. 1) l-amino-4- (methylamino) -9, 10-anthraquinone (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy-1, 4-naphthoquinone, 2, 5-dihydroxy-1, 4- naphthoquinone, 2-hydroxy-3-methyl-l, 4-naphthoquinone, N- (6- ((3-chloro-4- (methylamino) phenyl) imino) -4-methyl-3 -oxo-l, 4- cyclohexadien-l-yl) urea (HC REDNO. 9), 2- ((4- (di (2-hydroxyethyl) amino) phenyl) amino) -5- ((2-hydroxyethyl) amino ) -2, 5-cyclohexadiene-l, 4-dione (HC Green No. 1), 5-hydroxy-l, 4-naphthoquinone (CI75500, Natural BrownNo. 7), 2-hydroxy-l, 4-naphthoquinone (CI75480 , Natural Orange No. 6), l, 2-dihydro-2- (1, 3- dihydro-3-oxo-2H-indol-2-ylidene) -3H-indol-3-one (CI73000), 4- ( (5- ((2-hydroxyethyl) amino-l-methyl-lH-pyrazol-4-yl) imino) -4,5-dihydro-5- ((2-hydroxyethyl) imino) -1-methyl-IH-pyrazole - sulfate (1: 1), hydrate (1: 1).

Basic dyes:

9- (dimethylamino) benzo [a] phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), di [4- (diethylamino) phenyl] [4- (ethyl- amino) naphthyl] carbenium-chloride ( CI42595; Basic Blue No. 7), di (4- (dimethylamino) phenyl) - (4- (methylphenylamino) naphthalen-1-yl) - carbenium chloride (CI42563; Basic Blue No. 8), 3, 7-

Di (dimethylamino) phenothiazin-5-ium chloride (CI52015 Basic Blue No. 9), di [4- (dimethylamino) phenyl] [4- (phenyl- amino) naphthyl] carbenium chloride (CI44045; Basic Blue No. 26 ), 2- [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methyl-benzothiazolium-methylsulfate (CI11154; Basic Blue No. 41), 8-amino-2-bromo -5-hydroxy-4-imino-6- [(3-

(Trimethylammonio) phenyl) amino] -1 (4H) -naphthalinon- chloride (CI56059; Basic Blue No. 99), bis [4- (dimethylamino) phenyl] [4- (methylamino) phenyl] carbenium chloride (CI42535; Basic Violet No. 1), tri (4-amino-3-methylphenyl) carbenium chloride (CI42520; Basic Violet No. 2), tris [4- (dimethylamino) phenyl] carbenium chloride (CI42555; Basic Violet No. 3). , 2- [3,6-

(Diethylamino) dibenzopyranium-9-yl] benzoyl chloride (CI45170, - Basic Violet No. 10), di (4-aminophenyl) (4-amino-3- methylphenyl) carbeniumchlorid (CI42510 Basic Violet No. 14), 1,3 - bis [(2,4-diamino-5-methylphenyl) azo] -3-methylbenzene (CI21010; Basic Brown No. 4), 1- [(4-aminophenyl) azo] -7- (trimethylammonio) -2-naphthol - chloride (CI12250; Basic Brown No. 16), 3- [(4-amino-2, 5-dimethoxyphenyl) azo] -N, N, N-trimethylbenzolaminiumchlorid

(CI112605, Basic Orange No. 69), 1- [(4-amino-2-nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol chloride, 1- [(4-amino-3-nitrophenyl) azo ] -7- (trimethylammonio) -2-naphthol chloride (CI12251; Basic Brown No. 17), 3, 7-diamino-2, 8-dimethyl-5-phenylphenazinium- chloride (CI50240; Basic Red No. 2), l, 4-dimethyl-5- [(4- (dimethyl- amino) phenyl) azo] -1,2, 4-triazolium chloride (CI11055; Basic Red No. 22), 2-hydroxy-l- [(2 methoxyphenyl) azo] -7 (trimethylammonio) - naphthalene chloride (CI12245; Basic Red No. 76) 2- [2- ((2,4-dimethoxyphenyl) amino) ethenyl] - 1,3,3-trimethyl -3H-indol-l-ium- chloride (CI48055; Basic Yellow No. 11), 3 -methyl -1 -phenyl -4- [(3- (trimethylammonio) phenyl) azo] -pyrazol-5-one hydrochloride ( CI12719; Basic Yellow No. 57), di [4- (dimethylamino) phenyl] iminomethan- hydrochloride (CI41000; Basic Yellow No. 2), bis [4- (diethylamino) phenyl] phenyl carbenium hydrogensulf at (1: 1) (CI42040; Basic Green No. 1), di (4- (dimethylamino) phenyl) - phenylmet HANOL (CI42000; Basic Green No. 4) l- (2-

Morpholiniumpropylamino) -4-hydroxy-9, 10-anthraquinone methylsulfate, 1- [(3- (dimethyl-propylaminium) propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride. Neutral azo dyes:

1- [di (2-hydroxyethyl) amino] -3-methyl-4- [(4-nitrophenyl) azo] benzene

(CI11210, Disperse Red No. 17), 1- [di (2-hydroxyethyl) amino] -4- [(4-nitrophenyl) azo] benzene (Disperse Black No. 9), 4- [(4-aminophenyl) azo] -1- [di (2-hydroxyethyl) amino] -3-methylbenzene (HC Yellow No. 7), 2, 6-diamino-3- [(pyridin-3-yl) azo] pyridine, 2- ( (4-

(Acetylamino) -phenyl) azo) -4-ethylphenol (CI11855; Disperse Yellow No. 3).

Acid dyes:

6-hydroxy-5- [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CI15985; Food Yellow No. 3;. FD & C Yellow No. 6), 2,4-dinitro-l-naphthol-7-sulfonic acid disodium salt (CI10316; Acid Yellow No. 1; Food Yellow No. 1), 2- (indane-1, 3-dione-2-yl) (quinolin-x, x-sulfonic acid (mixture of mono- and disulfonic acid) CI47005; D & C Yellow No. 10; Food Yellow No. 13;. acid Yellow No. 3), 5-hydroxy-l- (4-sulfop enyl) -4- [(4-sulfophenyl) azo] pyrazole-3-carboxylic acid trisodium salt ( CI19140; Food Yellow No. 4; Acid Yellow No. 23), 9- (2-carboxyphenyl) -6-hydroxy-3H-xanthen-3-one

(CI45350; Acid Yellow No. 73; D & C Yellow No. 8), 4- ((4-amino-3-sulfophenyl) azo) benzenesulfonic acid disodium salt (CI13015, Acid Yellow No. 9), 5- [(2,4 -dinitrophenyl) amino] -2-phenylamino-benzenesulfonic acid sodium salt (CI10385; Acid Orange No. 3), 4- [(2, 4-dihydroxyphenyl) azo] -benzenesulfonic acid, monosodium salt (CI14270; Acid Orange No. 6), 4-. [(2-hydroxynaphth-l-yl) azo] - benzenesulfonic acid sodium salt (CI15510; Acid Orange No. 7), 4- [(2, 4-dihydroxy-3- [(2, 4-dimethylphenyl) azo] phenyl) azo] - benzenesulfonic acid sodium salt (CI20170; Acid Orange No. 24), 4-hydroxy-3- [(4-sulphonaphth-l-yl) azo] -1-naphthalene-sulfonic acid disodium salt (CI14720; Acid Red No fourteenth ), 4-hydroxy-3- [(2-methoxy-phenyl) azo] -1-naphthalenesulfonic acid monosodium salt (CI14710; Acid Red No. 4), 6-hydroxy-5- [(4-sulphonaphth-1-yl) azo] -2, 4-naphthalene-disulfonic acid trisodium salt (CI16255; Ponceau 4R; Acid Red No. 18), 3-hydroxy-4- [(4-sulphonaphth-l-yl) azo] -2, 7-naphthalene d isulfonsäure acid trisodium salt (CI16185; Acid Red No. 27), 8-amino-l-hydroxy-2- (phenylazo) -3, 6-naphthalene disulfonic acid disodium salt (CI17200;. Acid Red No. 33), 5- (acetylamino) -4-hydroxy-3- [( 2-methylphenyl) azo] -2, 7-naphthalene-disulfonic acid disodium salt (CI18065; Acid Red No. 35), 2- (3-hydroxy-2, 4, 5, 7-tetraiod- dibenzopyran-6-on-9 -yl) -benzoic acid disodium salt (CI45430; Acid Red No. 51), N- [6- (diethylamino) -9- (2, 4-disulfophenyl) -3H-xanthen-3 -ylidene] -N-ethylethanammonium hydroxide , inner salt, sodium salt (CI45100;. Acid Red No. 52) 8- [(4- (phenylazo) phenyl) azo] -7-naphthol-1, 3-disulfonic acid disodium salt (CI27290; Acid REDNO 73rd), 2 ', 4', 5 ', 7' -Tetrabrom-3 ', 6' -dihydroxyspiro [isobenzofuran1 (3H), 9 '- [9H] anthen] -3-one disodium salt (CI45380 Acid Red No. 87) , 2 ', 4', 5 ', 7 <-Tetrabrom-4, 5,6,7-tetrachloro-3', 6'-dihydroxyspiro [isobenzofuran-1 (3H), 9 '[9H] xanthene] -3 on- disodium salt (CI45410; Acid Red No. 92), 3 ■, 6 '-dihydroxy-4', 5 '- diiodospiro [isobenzofuran -1 (3H), 9 '(9H) xanthen] -3 -one-disodium salt (CI45425; Acid Red No. 95) 2-hydroxy-3- ((2-hydroxynaphth-l-yl) azo) -5-nitrobenzenesulfonic acid monosodium salt (CI15685; Acid Red No. 184), (2-sulfophenyl) di [4- (ethyl (( 4- sulfophenyl) methyl) amino) phenyl] -carbenium disodium salt, betaine (CI42090; Acid Blue No. 9;. FD & C Blue No. 1), 1, 4-bis [(2-sulfo-4-methylphenyl) amino] -9 , 10-anthraquinone disodium salt (. Cl 61570; Acid Green No. 25), bis [4- (dimethylamino) phenyl] - (3, 7-disulfo-2-hydroxynaphth-1-yl) carbenium inner salt, monosodium salt (CI44090; Food Green No. 4;. Acid Green No. 50), bis [4-.

(Diethylamino) phenyl] (2, 4-disulfophenyl) carbenium inner salt, sodium salt (2: 1) (.. CI42045; Food Blue No. 3; Acid Blue No. 1), bis [4- (diethylamino) phenyl] (5 -hydroxy-2, 4-disulfophenyl) carbenium inner salt, calcium salt (2: 1) (CI42051; Acid Blue No. 3), 1- amino-4- (cyclohexylamino) -9, 10-anthraquinone-2-sulfonic acid sodium salt (CI62045; Acid Blue No. 62), l-amino-4- (phenylamino) - 9, 10-anthraquinone-2-sulfonic acid (CI62055; Acid Blue No. 25), 2- (1, 3-dihydro-3 -oxo-5-sulfo-2H-indol-2-ylidene) -2, 3-dihydro-3-oxo-lH-indole-5-sulfonic acid disodium salt (CI73015; Acid Blue No. 74), 9- (2- carboxyphenyl) -3- [(2-methylphenyl) amino] -6- [(2-methyl-4- sulfophenyl) mino] xanthylium inner salt, monosodium salt (CI45190;. Acid Violet No. 9), l-hydroxy-4- [(4-methyl-2-sulfophenyl) amino] -9, 10-anthraquinone sodium salt (CI60730; D & C Violet No. 2;. Acid Violet No. 43), bis [3-nitro-4- [4- (phenylamino) -3-sulfo-phenylamino] phenyl] sulfone (CI10410; Acid Brown No. 13), 5-amino-4-hydroxy-6- [(4-nitrophenyl) azo] -3- (phenylazo) -2, 7-naphthalene-disulfonic acid disodium salt (CI20470; Acid Black No. 1), 3-hydroxy-4- [(2-hydroxynaphth-l-yl) azo] -7-nitro-1-naphthalene-sulfonic acid-chromium complex (3: (2) CI15711; Acid Black No. 52), 3- [(2, 4-dimethyl-5-sulfophenyl) azo] -4-hydroxy-l-naphthalene-sulfonic acid disodium salt (CI14700; Food Red No. 1; Ponceau SX; FD & C Red No. 4), 4- (acetylamino) -5-hydroxy-6- [(7-sulfo-4- [(4-sulfophenyl) azo] naphth-1-yl) azo] -1, 7- naphthalenedisulfonic acid tetrasodium salt (CI28440; Food Black No. 1), 3 -hydroxy-4- (3-methyl-5-oxo-l-phenyl-4, 5-dihydro-lH-pyrazol-4-ylazo) naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red No. 195 ).

Other well-known for hair coloring and customary dyes that may be included colorants of the invention are, among others, E. Sagarin, "Cosmeties, Science and Technology", Interscience Publishers Inc., New York (1957), pages 503 et seq., And H . Janistyn, "Handbook of cosmetics and fragrances", Volume 3 (1973), pages 388 et seq. and K. Schrader "principles and

Formulations of Cosmetics ", 2nd Edition (1989), pages 782-815 described.

Suitable hair-coloring pigments are practically insoluble colorants in the application medium and can be inorganic or organic. Also inorganic-organic mixed pigments are possible. The pigments are preferably not nanopigments. The preferred particle size is 1 to 200 microns, particularly 3 to 150 microns, more preferably 10 to 100 μm.Bevorzugt are inorganic pigments. The inorganic pigments can be of natural origin, for example chalk, ocher, umber, green earth, burnt sienna or graphite. The pigments may be white pigments such as titanium dioxide or zinc oxide, black pigments such as iron oxide black, colored pigments, such as ultramarine or iron oxide, to act luster pigments, metal effect pigments, pearlescent pigments and fluorescent or phosphorescent pigments, where preferably at least one pigment is a colored is non-white pigment. Suitable metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates, and the metals themselves (bronze pigments). Suitable titanium dioxide are especially (Cl 77891), black iron oxide (Cl 77499), yellow iron oxide (Cl

77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium Aluminiumsulfosilikate, Cl 77007, Pigment Blue 29), chromium oxide hydrate (CI77289), iron blue (ferric ferrocyanide, CI77510), carmine (cochineal). Particularly preferred pigments, mica or mica are which are etc. coated with a metal oxide or a metal such as titanium dioxide or bismuth oxychloride, and optionally further color-imparting substances such as iron oxides, iron blue, ultramarine, carmine, and wherein the color is determined by varying the layer thickness. Such pigments are marketed under the trade name Rona, Colorona®, Dichrona® and Timiron® by Merck, Germany. Organic pigments are, for example, the natural pigments sepia, cambogia, bone charcoal, Cassel brown, indigo, chlorophyll and other plant pigments. Synthetic organic pigments are azo pigments, anthraquinoid, indigoid, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, Alkaliblau- and diketopyrrolopyrrole pigments. 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 from 0.05 to 5.%. Preferred hair conditioning agents are silicone compounds, and cation-active substances, which, because of cationic or cationizable groups, especially primary, secondary, tertiary or quaternary amine groups, a substantivity to human hair. Suitable cation-active materials are selected from cationic surfactants, betaine amphoteric surfactants, cationic polymers, silicone compounds containing cationic or cationizable groups, cationically derivatized proteins or protein hydrolyzates and betaine.

Suitable silicone compounds are polydimethylsiloxane (INCI: Dimethicone), α-hydro-ω-hydroxypolyoxydimethylsilylen (INCI: dimethiconol), cyclic dimethylpolysiloxane (INCI: cyclomethicone), trimethyl (octadecyloxy) silane (INCI: Stearoxy- trimethylsilane), dimethylsiloxane / glycol copolymer ( INCI: dimethicone copolyol), dimethylsiloxane / aminoalkylsiloxane copolymer (hydroxy-INCI: amodimethicone), monomethylpolysiloxane with Laurylseitenketten and polyoxyethylene and / or Polyoxypropylenendketten, (INCI: laurylmethicone copolyol), dimethylsiloxane / glycol Copolymeracetat (INCI: dimethicone copolyol acetate), dimethylsiloxane / aminoalkylsiloxane copolymer

Trimethylsilyl (INCI: trimethyl). Preferred silicone polymers are dimethicone, cyclomethicone and dimethiconols. Mixtures of silicone polymers are suitable, such as a mixture of dimethicone and dimethiconol. The names given above in brackets refer to the

INCI nomenclature (International Cosmetic Ingredients), as they are intended for labeling of cosmetic active ingredients and excipients. Usually, other known additives may cosmetic hair treatment agent according to the invention be added, for example, non-fixing, nonionic polymers such as polyethylene glycols, non-fixing, anionic and natural polymers and mixtures thereof in an amount of preferably 0.01 to 50 wt.%. Also, perfume oils in an amount of 0.01 to 5.%, Opacifiers such as ethylene glycol in an amount of 0.01 to 5 wt.%, Wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols,

Fatty acid esters of hydrogenated castor oil as used in an amount of 0.1 to 30.%, Further humectants, tinting agents, light stabilizers, antioxidants and preservatives in an amount of 0.01 to 10 wt.%.

1 shows schematically the process for producing a triggerable permanent shape. A strand of hair is wound on a bobbin and sprayed with a present invention, a cross-linkable macromer-containing solution. By

Irradiation of a suitable energy source such as a UV lamp is fixed, the desired permanent shape. Finally, the winding body is removed.

Figure 2 shows the deformation of a permanent shape and recovery of the permanent shape from the temporary shape. The lock of hair in the permanent shape has the length lo • The curl in the deformed shape has lχ the length. The curl in the recovered shape has length I2 • The degree of recovery (recovery) is calculated by: Recovery = dl - 12) / dl - lo) •

As a measure for assessing the shape memory properties of a composition of the memory factor can be used, in which both the formability of a permanent hairstyle into a temporary shape (form factor) as well as the recovery of the permanent shape from the temporary shape (restoration factor, degree of recovery) are considered. It is assumed that a smooth streak to a curly shape has been impressed as a permanent shape and then a second, smooth shape has been impressed as a temporary shape to, the form 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 shape factor f, the maximum shape factor F = 4, the respective reset factor r and the maximum restoration factor R = 6 according to

M = (f / F) * (r / R) * 100 The Memory factor should not be less than 25, ideally, preferably between 25 and 33.3, more preferably between 37 to 100.

The following examples illustrate the present invention. Examples Example 1: Hair treatment with a thermoset shape memory polymer

prepared according to Example 2 of WO 99/42147

To smooth hair strands of a length of 19 cm per approximately 1 g of

Composition is applied. The tresses were wound on curlers and dried. (Hg lamp or facial UV) light cured C was then applied to approximately 65 to 70 ° and heated photochemically. After curing and cooling to room temperature, the rollers were removed. The curls (impressed permanent mold) had a length of 8 cm.

In order to simulate deformation by cold deformation, the curls were loaded with a weight of 25 g and a), b) 2 hours, and c) unhooked 1 hour 3 hours at room temperature. The lengths of the curls after deformation were a) 10 cm, b) 10 cm and c) 11.2 cm.

After removing the weights was heated to about 65-70 ° C. The curls subjected spontaneously together to lengths of a) 8 cm, b) 8 cm and c) 8.3 cm. This corresponds to restore levels of the impressed hairstyle of a) 100%, b) 100% and c) 91%. The degree of recovery (recovery) is calculated according to (see FIG. 2): Recovery = dl - 1 2) / dl - lo)

For impressing a second hairstyle (temporary shape), a curled strand (Locke) a length of 3.2 cm to about 65- 70 ° C heated, stretched to their original, full length of 6.3 cm and cooled. With renewed heating to about 65-70 ° C, the Locke pulled together spontaneously to a length of 3.9 cm. This corresponds to a degree of recovery of the impressed hairstyle of 77%.

Examples 2 to 31: Hair treatment with shape memory polymer

Were prepared from each 2 weight compositions.% Macromer in an ethanol / water mixture (50/50) 'with the following macromers or Macromermischungen with the following weight ratios

The application of the compositions 2 to 31 were effected as described with similar results as in Example 1. "

Examples 32 to 41: Hair treatment with shape memory polymer

Were prepared from each 2 wt% macromer compositions in THF with the following macromers or Macromermischungen with the following weight ratios.:

The application of the compositions 32 to 41 performed as described, with similar results as in Example. 1

Example 42: Hair treatment with shape memory polymer

A composition was prepared from 2 wt.% PLGA (7k) -DMA macromer in ethyl acetate and applied to the hair. After the hair was placed in mold, the mold was fixed by irradiation with UV light. The preparation of the macromers used in Examples 2-42 was carried out analogously as described in WO 99/42147 described.

The abbreviations used in the examples are: PEG (4k) -DMA, PEG (8k) -DMA, PEG (10k) -DMA: Poly (ethylene glycol) dimethacrylate PPG (475) -MA, PPG (430) -MA poly (propylene glycol) methacrylate, PEG (526) -MA: poly (ethylene glycol) methacrylate NθO-PPG (400) -MA, Noo-PPG (475) -MA: nonyl-poly (propylene glycol) methacrylate

MeO-PEG- (300) -MA: methyl-poly (ethylene glycol) methacrylate-MeO PPG (200) -MA: methyl-poly (propylene glycol) methacrylate PLGA (7k) -DMA: Poly (L-lactide-co- glycolide) dimethacrylate PCI (10k) -DMA: poly (ε-caprolactone) dimethacrylate

Claims

claims
1. A method for hair treatment, wherein
- a composition comprising at least one crosslinkable macromer forming a shape memory polymer after cross-linking is applied to the hair, wherein the macromer a) contains cross-linkable regions that by chemical
Bonds can be crosslinked and b) contain thermoplastic regions that are not chemically crosslinked, before, simultaneously or subsequently the hair is brought into a specific (continuous) form, and then the shape is fixed by chemical crosslinking of the macromer to form the shape memory polymer, wherein the having shape memory polymer at least one transition temperature T ans.
2. The method for hair treatment, wherein - a programmed by a method according to claim 1
Hairstyle (permanent shape) is heated to a temperature above T trans, the hair is brought into a second (temporary) shape and the second shape is fixed by cooling to a temperature below T trans.
3. A process for the recovery of a previously programmed by a method according to claim 1 hairstyle (permanent shape), wherein a hairstyle in a temporary shape according to claim 2 or deformed by cold deformation of hair is heated to a temperature above T trans.
4. The method according to any one of the preceding claims, characterized in that the crosslinkable macromer is selected from compounds of the general formula
Al (X) n -A2 (I) wherein Al and A2 represent reactive, chemically cross-linkable groups and - (X) n- represents a divalent, thermoplastic polymer or oligomer.
5. The method according to claim 4, characterized in that the crosslinkable macromer is selected from at least two
Acrylate or methacrylate substituted polyesters, oligoesters, polyalkylene glycols, oligo alkylene glycols, polyalkylene carbonates and Oligoalkylencarbonaten.
6. The method according to claim 5, characterized in that the crosslinkable macromer is selected from poly (ε-caprolactone) - dimethacrylate, poly dimethacrylate (DL-lactide), poly (L-lactide-co-glycolide) dimethacrylate, poly ( ethylene glycol) dimethacrylate, poly (propylene glycol) dimethacrylate, PEG-block-PPG-PEG block-dimethacrylate, poly (ethylene adipate) dimethacrylate, Hexamethylencarbonatdimethacrylat.
7. 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 is contained.
8. The method according to claim 7, characterized in that the additional macromer is selected from compounds of the general formula
R- (X ') n -A3 (II) where R is a monovalent organic residue, A3 designates a reactive, chemically cross-linkable group and - (X' stands) n designates a divalent, thermoplastic polymer or oligomer.
9. The method according to claim 8, characterized in that the additional macromer is selected from a polyalkylene-substituted acrylate or methacrylate, their monoalkyl ethers and block copolymers thereof.
10. The method according to claim 9, characterized in that the additional, substituted with only one chemically reactive group macromer is selected from poly (ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate, and their monoalkyl ethers.
11. A cosmetic composition) containing containing, in a suitable cosmetic base at least one crosslinkable to a shape memory polymer macromer, wherein the shape memory polymer comprises at least one transition temperature τ trans and wherein the macromer a) contains cross-linkable regions that are cross-linkable through chemical bonds and b thermoplastic areas, which are not chemically cross-linked.
12. The composition according to claim 11, characterized in that the crosslinkable macromer to from 0.01 to 25 wt.% Is included.
13. The composition according to any one of claims 11 to 12, characterized in that additionally 0.01 to 25 wt.% Of at least one additional macromer with only one terminal or pendant, chemically reactive group and / or at least one active ingredient selected from haircare substances , hair-setting substances and hair-coloring substances contained.
14. A cosmetic composition comprising a composition according to any one of claims 11 to 13, characterized in that it aerosol sprays in the form of a lotion, a spray lotion, a cream, a gel, a Gelschaums, an aerosol spray, a Non-, an aerosol foam, a non -aerosolschaums, an O / W or W / O emulsion, a microemulsion or a hair wax is present.
15. Use of crosslinkable macromers to shape memory polymers for hair treatment, wherein the macromers comprise a) crosslinkable areas by chemical
Bonds can be crosslinked and b) contain thermoplastic regions that are not chemically vernetsbar and wherein the shape memory polymers contain at least one transition temperature T trans.
EP20030724998 2002-04-10 2003-04-10 Method for treating hair with form memory polymers Withdrawn EP1492494A1 (en)

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US20060088494A1 (en) 2006-04-27 application
WO2003084491A1 (en) 2003-10-16 application

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