EP1492493A1 - Method for the generation of memory effects on hair - Google Patents

Method for the generation of memory effects on hair

Info

Publication number
EP1492493A1
EP1492493A1 EP03724997A EP03724997A EP1492493A1 EP 1492493 A1 EP1492493 A1 EP 1492493A1 EP 03724997 A EP03724997 A EP 03724997A EP 03724997 A EP03724997 A EP 03724997A EP 1492493 A1 EP1492493 A1 EP 1492493A1
Authority
EP
European Patent Office
Prior art keywords
hair
shape
shape memory
amino
poly
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Withdrawn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
EP03724997A
Other languages
German (de)
French (fr)
Inventor
Andreas Lendlein
Werner Grasser
Karl Kratz
Thomas Krause
Axel Kalbfleisch
Günther LANG
Jürgen Allwohn
Johannes Burghaus
Gerhard Sendelbach
Detlef Mattinger
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
Original Assignee
MnemoScience GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE10215858A external-priority patent/DE10215858A1/en
Priority claimed from DE2002128120 external-priority patent/DE10228120B4/en
Application filed by MnemoScience GmbH filed Critical MnemoScience GmbH
Publication of EP1492493A1 publication Critical patent/EP1492493A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry 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 TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry 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 TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry 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 TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry 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 TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry 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 TOILETRY 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 TOILETRY 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

Definitions

  • the present invention relates to a method for achieving a retrievable hair remodeling using active ingredients which impart a shape memory effect to the hair, in particular of macromers which can be crosslinked to shape memory polymers or of shape memory polymers.
  • Temporary hair shaping is usually carried out using compositions based on solutions or dispersions of hair-fixing polymers. Such products give the hair more or less hold, volume, elasticity, bounce and shine through the addition of polymer.
  • Styling products facilitate the shaping and creation of the hairstyle as a gel, improve the status of a hairstyle as a hairspray 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 is usually done by permanent wave treatment. Here, disulfide bonds in the hair are reductively split, the hair is brought into the new shape and fixed by oxidative formation of new disulfide bonds. It is disadvantageous that the necessary chemical treatment of the hair with reducing and oxidizing agents cannot impair the structure of the hair.
  • JP 04-41416 discloses hair cosmetics which contain certain linear polyurethanes with a glass transition temperature Tg of 40-90 ° C.
  • Tg glass transition temperature
  • the object underlying the present invention was to provide a method and the products required for a retrievable, in particular for a repeatedly retrievable hair shaping with a high degree of restoration of a programmed hairstyle shape. Another object was to provide a method with which it is possible to achieve permanent hair styling without damaging the structure of the hair. Another task was to provide a method which makes it possible to easily undo temporary reshapings several times and to return to a previously created, programmed, permanent hairstyle shape with high accuracy. 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 ingredient composition is applied to the hair, the active ingredient composition containing at least one active ingredient which is selected from substances which, alone or in combination with other substances, are capable of applying to the hair after application to the hair and after the treatment described below to give a shape memory effect; 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 the memory form is then 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.
  • a particular embodiment relates to a method for hair treatment, wherein - a composition which has at least one crosslinkable
  • Macromer which forms a shape memory polymer after crosslinking, is applied to the hair, the macromer containing a) crosslinkable regions that can be crosslinked by chemical bonds and b) thermoplastic regions that are not chemically crosslinkable, before, at the same time or subsequently, the hair is brought into a specific (permanent) shape 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.
  • 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
  • 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 they can be imprinted with any shape (permanent shape), into which they spontaneously and after deformation or after being imprinted with a second shape (temporary shape) convert back without external force by just warming up or by another energetic stimulus. Deformation and reconversion are 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 in the following
  • the degree of reconversion in the first relaxation cycle is preferably at least 30%, particularly preferably at least 50% and in the subsequent relaxation cycles preferably at least 60%, particularly preferred 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 merely heating or by another energetic stimulus, i.e. preferably at least 30 in a first relaxation cycle %, 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 linked to one another by chemical bonds.
  • Crosslinking via chemical bonds can take place via ionic or covalent bonds.
  • the crosslinking reaction can be any chemical reaction, e.g. 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, e.g. through 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.
  • T trans the polymer has a lower modulus of elasticity than below Ttrans- Since s lower ratio of the elasticity modules and Ttrans i above st preferably at least 20.
  • the transition temperature Ttrans 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 de-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 is networked and fixed in a permanent form
  • Shape memory polymers have a certain shape.
  • Restoring a programmed hairstyle in the sense of the invention means that after a deformation the programmed hairstyle regresses again preferably 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.
  • Macromers or prepolymers are macromonomers that can be polymerized or cross-linked 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. So there are switching segments and Network points are required, with 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 exceeds or falls below.
  • the ratio of the elasticity modules below and above Ttrans is preferably at least 20.
  • thermoset polymers with shape memory properties there are four types of thermoset polymers with shape memory properties: network polymers, penetrating networks, semi-penetrating networks and mixed-penetrating networks.
  • Network polymers can be formed by covalently linking macromonomers, ie 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.
  • Pervasive networks are formed from at least two components, each of which 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.
  • 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 represents 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 ( ⁇ -caprolactones), oligo- or polylactides, oligo- or polyalkylene glycols, for example
  • Polyethylene or polypropylene glycol or their block copolymers the polymers or oligomers mentioned being substituted in the end or laterally with at least two free-radically polymerizable, ethylenically unsaturated groups, for example acrylates or methacrylates.
  • the polymer segments can be segments derived from natural polymers such as proteins or polysaccharides. 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 (ß-hydroxybutyrate) ), Poly (3-hydroxyoctanoate) or poly (3-hydroxy fatty acids). Derivatives of natural polymer segments, for example alkylated, hydroxyalkylated, hydroxylated or oxidized modifications, are also suitable.
  • Synthetically modified natural polymers are, for example, cellulose derivatives such as alkyl celluloses, hydroxyalkyl celluloses, cellulose loose ethers, cellulose esters, nitrocelluloses, chitosan or chitosan derivatives, which are obtained for example by N- or / and O-alkyl or hydroxyalkyl substitution.
  • cellulose derivatives such as alkyl celluloses, hydroxyalkyl celluloses, cellulose loose ethers, cellulose esters, nitrocelluloses, chitosan or chitosan derivatives, which are obtained for example by N- or / and O-alkyl or hydroxyalkyl substitution.
  • 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 tri
  • 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.
  • suitable polyacrylates are poly (methyl methacrylate), poly (ethyl methacrylate), poly (butyl methacrylate),
  • 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- ( ⁇ -caprolactone)]; Poly [glycolide-co- ( ⁇ -caprolactone)]; Polycarbonates, poly (amino acids); Poly (hydroxyalkanoates), polyanhydrides; Polyorthoesters and their mixtures and copolymers.
  • poorly biodegradable polymer segments are poly (methacrylic acid), poly (acrylic acid), polyamides, polyethylene, polypropylene, polystyrene, Polyvinyl chloride, polyvinylphenol and their mixtures and copolymers.
  • 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, for example, those of the general formula R- (X ') n -A3 (II) where R for a monovalent organic radical, A3 for a reactive, chemically crosslinkable group and - (X') n- for a divalent, thermoplastic Polymer or oligomer segment stands.
  • 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
  • component (A) poly ( ⁇ -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.
  • component (B) are, for example: poly (ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate and their monoalkyl ether. Another special embodiment relates to a method for
  • composition which contains at least one shape memory polymer is applied to the hair, the shape memory polymer having at least two transition temperatures
  • Ttrans un & ⁇ 'trans and a) at least one hard segment which can be crosslinked by physical interaction with 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 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 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 T rans » which is below T'trans», preferably at least 10 ° C below T'trans, has - before, at the same time or subsequently, the hair is brought into a specific (permanent) shape and then the shape by physical crosslinking the shape memory polymer is fixed.
  • the hair is expediently shaped with heating to a temperature of at least T'trans and the hair shape is fixed by cooling to a temperature below T'trans.
  • 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
  • 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 embossing a second hairstyle shape on a programmed, retrievable first hairstyle shape.
  • a hairstyle (permanent shape) programmed by the above-mentioned method is first heated to a temperature between T'trans un ( 3 Ttrans). The hair is then brought into the desired second (temporary) shape and the second shape is cooled to a Fixed 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.
  • 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, e.g. by simply unhooking the curls under the influence of gravity, by combing or brushing the hair, by wind or moisture, by mechanical influences while sleeping or lying down 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.
  • the original hairstyle is heated to a temperature above T'trans and the hair is brought into a new shape.
  • the new shape is then fixed by cooling to a temperature below T'trans.
  • physically crosslinkable shape memory polymers are polymers in which the impressed permanent shape is fixed by crosslinking on the basis of physical interactions.
  • Networking 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 formation of the interactions can be triggered, for example, by cooling (in particular in the case of crystallizations) and / or by drying, ie by removing solvents.
  • Physically crosslinkable shape memory polymers suitable according to the invention have at least two transition temperatures Ttrans and d T'trans. Both transition temperatures can be, for example, melting temperatures T m or glass transition temperatures Tg. Above T trans, the polymer has a lower modulus of elasticity than below Ttrans • lower the ratio of the elasticity modules and Ttrans above st preferably at least 10, more preferably at least 20.
  • the lower transition temperature Ttrans i st 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'trans is via Ttrans and 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 Ttrans 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'trans is preferably at least 10 ° C, particularly preferably at least 20 ° C or at least 30 ° C above Ttrans-D difference between T'trans and Ttrans can be, for example, from 10 to 80 ° C, from 20 to 70 ° C or from 30 to 60 ° C. Suitable ranges for T'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 soft segment.
  • the hard segment has physical cross-links and has a transition temperature T'trans ° Lie above room temperature, preferably more than 10 ° C above 20 ° C.
  • the soft segment has a transition temperature Ttra s »which is below T'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 ,
  • thermoplastic polymers 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
  • 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, 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.
  • 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 ⁇ , ⁇ -dihydroxy-polyesters, ⁇ , ⁇ -dihydroxy-oligoesters, ⁇ , ⁇ -dihydroxy-polylactones and ⁇ , ⁇ -dihydroxy-oligolactones and (b) at least one diisocyanate, preferably trimethylhexane-1,6-diisocyanate.
  • two different macrodiols selected from ⁇ , ⁇ -dihydroxy-polyesters, ⁇ , ⁇ -dihydroxy-oligoesters, ⁇ , ⁇ -dihydroxy-polylactones and ⁇ , ⁇ -dihydroxy-oligolactones
  • at least one diisocyanate preferably trimethylhexane-1,6-diisocyanate.
  • Macrodiols made from poly (para-dioxanone) (PDX), poly (pentadecalactone) (PDL), poly ( ⁇ -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 polydispersities are preferably in the range from 1.7 to 2.0.
  • a further particular embodiment relates to a method for hair treatment using an active ingredient composition which contains at least two active ingredients which individually have no or only weak shape memory properties and which, when used together in accordance with the abovementioned methods, give hair a synergistically increased shape memory effect.
  • compositions according to the invention for hair treatment contain at least one active ingredient which brings about a shape memory effect on hair in an amount of preferably from 0.01 to 25% by weight, particularly preferably from 0.1 to 15% by weight, in a suitable medium.
  • the composition can be in the form of a solution, dispersion, emulsion, suspension or latex.
  • the liquid, gel-like, semi-solid or solid medium is essentially cosmetically acceptable and physiologically harmless.
  • 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 e.g. aliphatic Cl to C4 alcohols or a mixture of water with one of these alcohols.
  • other organic solvents can also be used, in particular unbranched or branched hydrocarbons such as pentane, hexane, isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane, organic linear or cyclic ethers, e.g. Tetrahydrofuran (THF) or liquid organic esters, e.g. Ethyl acetate should be mentioned.
  • THF Tetrahydrofuran
  • silicone-based solvents are also suitable, in particular silicone oils based on linear or cyclic polydimethylsiloxanes (dimethicone or cyclomethicone).
  • the solvents are preferably present in an amount of 0.5 to 99% by weight, particularly preferably in an amount of 40 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 by the addition of other polymers with thickening effect in its hair-setting properties be modified.
  • film-forming, hair-fixing polymers are understood to mean those polymers which, when used in 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, or polyethyleneglycols, polyvinyl alcohols up to 20,000 g / mol can be used.
  • Suitable synthetic, film-forming anionic polymers should be mentioned
  • 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 are particularly useful as copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone / dimethylaminomethacrylate copolymers quaternized with diethyl sulfate.
  • cationic polymers include the copolymer of vinyl pyrrolidone with vinyl, the terpolymer of dimethyldiallyl 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, vinyl pyrrolidone / Methacrylamidopropyltrimethylammonium chloride copolymer and diquaternary polydimethylsiloxanes.
  • the consistency of the hair treatment composition according to the invention can be increased by adding thickeners.
  • 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 / 0- emulsion, a microemulsion or a hair wax.
  • 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 such as, for example, n-butane, isobutane and propane, or else mixtures thereof, and also dimethyl ether or fluorocarbons are used as blowing agents such as F 152a (1, 1-difluoroethane) or F 134 (tetrafluoroethane) and, furthermore, gaseous blowing agents such as N 2 , N2O and C0 2 and mixtures of the abovementioned blowing agents are suitable at the pressures under consideration.
  • 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 spray one
  • 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 one
  • 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 can be used, for example, as a suitable mechanical foaming device.
  • 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.
  • 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 a molecular weight of 800 to 20,000, preferably from 2,000 to 10,000 g / mol.
  • 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.
  • a cosmetically acceptable alcohol in front.
  • the lower C1 to C4 alcohols commonly used for cosmetic purposes such as e.g. Ethanol and isopropanol can be used.
  • 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 a quantity of 0.1 to 10% by weight or the required viscosity and creamy consistency is built up in a conventional manner by micelle formation with the aid of suitable emulsifiers, fatty acids, fatty alcohols, waxes etc.
  • the agent according to the invention is capable of simultaneously embossing a retrievable hairstyle as well as hair coloring.
  • the agent is then used as a coloring hair treatment agent, e.g. Formulated 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 are: Nitro dyes (blue):
  • 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), l-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-l- [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No.
  • Nitro dyes (yellow): 1,2-diamino-4-nitrobenzene (CI76020), 1,2-amino-2- [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1- (2-hydroxyethoxy) -2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 4), l - [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Yellow No.
  • Basic dyes 9- (dimethylamino) benzo [a] phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium -chloride (CI42595; Basic Blue No. 7), di- (4- (dimethylamino) phenyl) - (4- (methyl-phenylamino) naphthalene-l-yl) - carbenium chloride (CI42563; Basic Blue No. 8) , 3,7-Di (dimethylamino) phenothiazine-5-ium chloride (CI52015 Basic Blue No.
  • 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- (indan-1, 3-dion-2-yl) quinoline- x, x-sulfonic acid (mixture of mono- and disulfonic acid) (CI47005; D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow No.
  • 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. Both
  • Pigments are preferably not nanopigments.
  • the preferred particle size is 1 to 200 ⁇ m, in particular 3 to 150 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • Inorganic pigments are preferred.
  • the inorganic pigments can be of natural origin, for example made from chalk, ocher, U bra, green earth, burnt terra di Siena or graphite.
  • the pigments can 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 red, around luster pigments, metallic effect pigments, pearlescent pigments as well as around fluorescent or
  • Act phosphorescent pigments preferably at least one pigment being a colored, non-white pigment.
  • Metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates as well as the metals themselves (bronze pigments) are suitable.
  • Titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29 ), Chromium Oxide Hydrate (CI77289), Iron Blue (Ferric Ferrocyanide, CI77510), Carmine (Cochineal).
  • Pigments based on mica or mica are particularly preferred, which are coated with a metal oxide or a metal oxychloride such as titanium dioxide or bismuth oxychloride and optionally other colorants such as iron oxides, iron blue, ultramarine, carmine, etc., and the color is determined by varying the layer thickness.
  • Pigments of this type are sold, for example, under the trade names Rona, Colorona, Dichrona and Timiron by Merck, Germany.
  • Organic pigments are e.g. the natural pigments sepia, gum, bone char, Kasseler brown, indigo, chlorophyll and other plant pigments.
  • Synthetic organic pigments are e.g. Azo pigments, anthraquinones, indigoids,
  • 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 silicone compounds and cationic substances which are based on cationic or cationizable groups, especially primary, secondary, tertiary or quaternary amine groups have a substantivity to human hair.
  • Suitable cationic substances are selected from cationic surfactants, betaine, amphoteric surfactants, cationic polymers, silicone compounds with cationic or cationizable groups, cationically derivatized proteins or protein hydrolyzates and betaine.
  • Suitable silicone compounds are e.g. Polydimethylsiloxane (INCI: Dimethicone), ⁇ -Hydro- ⁇ -hydroxypolyoxydimethylsilylene (INCI: Dimethiconol), cyclic Dimethylpolysiloxan (INCI: Cyclomethicone), Trimethyl (octadecyloxy) silane (INCI: Stearoxy-trimethylsilane), DimethylsiloxyI / Dimethylethiliconol / INC ), dimethylsiloxane / aminoalkylsiloxane copolymer having hydroxyl end groups (INCI: amodimethicone), monomethylpolysiloxane with Lauryl frictionketten and polyoxyethylene and / or Polyoxypropylenendketten, (INCI: laurylmethicone copolyol), dimethylsiloxane / glycol Copolymeracetat (INCI: dimethicone copolyol
  • silicone polymers are dimethicones, cyclomethicones and dimethiconols. Mixtures of silicone polymers are also suitable, e.g. 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.
  • 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 from the classes of anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid alkanolamides such as the esters of hydrogenated castor oil fatty acids in an amount of 0.1 to 30% by weight, as well as humectants, coloring agents, light stabilizers, antioxidants and Preservatives in an amount of 0.01 to 10% by weight.
  • opacifiers such as ethylene glycol distearate in an amount of 0.01 to 5% by weight
  • Wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid
  • 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.
  • 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 shape has the length lo •
  • the curl in the deformed shape has the length l.
  • the curl in the restored form has the length 1 2 •
  • the curl in the permanent shape has the length lo •
  • the curl in the deformed shape has the length l.
  • the curl in the restored form has the length 1 2 •
  • the memory factor can be used as a measure for assessing the shape memory properties of a composition, taking into account both the formability of a permanent hairstyle shape into a temporary shape (form factor) and the resetting of the permanent shape from the temporary shape (reset factor, degree of restoration). 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:
  • M (f / F) * (r / R) * 100
  • the memory factor should ideally not be less than 25, preferably between 25 and 33.3, particularly preferably between 37 and 100.
  • Example 1 Hair treatment with a thermoset shape memory polymer
  • Approx. 1 g of the composition was applied to straight strands of hair each 19 cm in length.
  • the strands were wound on curlers and dried.
  • the mixture was then heated to approximately 65 to 70 ° C. and cured photochemically (UV light; mercury lamp or facial tanner). After curing and cooling to room temperature, the winders were removed.
  • the curls (stamped permanent shape) had a length of 8 cm.
  • the curls were weighed down with a weight of 25 g each and hung out a) 1 hour, b) 2 hours and c) 3 hours at room temperature.
  • the lengths of the curls after deformation were a) 10 cm, b) 10 cm and c) 11.2 cm.
  • Examples 2 to 31 Hair treatment with shape memory polymer Compositions were prepared from 2% by weight of macromer in an ethanol / water mixture (50/50) with the following macromers or macromer mixtures with the following weight ratios
  • compositions 2 to 31 were used as described in Example 1 with similar results.
  • compositions were produced from 2% by weight of macromer in THF with the following macromers or macromer mixtures with the following weight ratios:
  • compositions 32 to 41 were used as described in Example 1 with similar results.
  • a composition was prepared from 2% by weight PLGA (7k) -DMA macromer in ethyl acetate and applied to the hair. After the hair was shaped, the shape was fixed by irradiation with UV light.
  • the shape memory polymers were produced from two different macrodiols and trimethylhexane-1, 6-diisocaynate analogously to Example 1 of WO 99/42147.
  • the hair treatment compositions were made from 0.5 wt% multiblock copolymer in a suitable solvent or solvent mixture such as e.g. Water, ethanol, tetrahydrofuran, chloroform or mixtures of these solvents, in particular
  • Tetrahydrofuran, chloroform or a water / ethanol / THF mixture Tetrahydrofuran, chloroform or a water / ethanol / THF mixture.
  • PLGA poly (L-lactide-co-glycolide)
  • PCL poly ( ⁇ -caprolactone)
  • the numerals in the names of the macrodiols each represent the approximate molecular weight of the macrodiols ( ⁇ 100)

Abstract

A method for achieving a reproducible hair shape is disclosed in which a composition is applied to the hair which comprises at least one active agent which, alone or in combination with other materials, can give hair a form memory effect after application to the hair and after carrying out the method according to the invention. The hair is given a particular (permanent) form and said permanent form is fixed by inducing a chemical or physical transition in the applied agents, whereby after a desired or undesired deformation of the memory form, the original memory form may be regenerated by means of a physical stimulation. 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

Verfahren zur Erzeugung von Foπngdächtniseffekten auf Haaren Process for producing hair memory effects
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Erzielung einer abrufbaren Haarumformung unter Verwendung von Wirkstoffen, welche den Haaren einen Formgedächtnis-Effekt verleihen, insbesondere von zu Formgedächtnispolymeren vernetzbaren Makromeren oder von Formgedächtnispolymeren.The present invention relates to a method for achieving a retrievable hair remodeling using active ingredients which impart a shape memory effect to the hair, in particular of macromers which can be crosslinked to shape memory polymers or of shape memory polymers.
Bei der Formgebung von Haaren wird im allgemeinen zwischen temporärer und dauerhafter, permanenter Haarverformung unterschieden. Eine temporäre Haarverformung erfolgt in der Regel unter Verwendung von Zusammensetzungen auf Basis von Lösungen oder Dispersionen haarfestigender Polymere. Derartige Produkte verleihen den Haaren durch den Polymerzusatz mehr oder weniger Halt, Volumen, Elastizität, Sprungkraft und Glanz. DieseWhen shaping hair, a distinction is generally made between temporary and permanent, permanent hair shaping. Temporary hair shaping is usually carried out using compositions based on solutions or dispersions of hair-fixing polymers. Such products give the hair more or less hold, volume, elasticity, bounce and shine through the addition of polymer. This
Stylingprodukte erleichtern z.B. als Gel die Formgebung und Erstellung der Frisur, verbessern als Haarspray den Stand einer erstellten Frisur und erhöhen als Festigerschaum das Volumen des Haares. Nachteilig ist, dass die gewünschten Effekte nur von relativ kurzer Dauer sind und durch äußere Einflüsse wie Kämmen, Wind, hohe Luftfeuchtigkeit oder Kontakt mit Wasser rasch wieder verloren gehen. Eine permanente Haarverformung erfolgt in der Regel durch eine Dauerwellbehandlung. Hierbei werden Disulfidbindungen im Haar reduktiv gespalten, das Haar in die neue Form gebracht und durch oxidative Bildung neuer Disulfidbindungen fixiert. Nachteilig ist, dass durch die erforderliche chemische Behandlung des Haares mit Reduktions- und Oxidationsmitteln eine Beeinträchtigung der Haarstruktur nicht vermieden werden kann. Ein weiterer Nachteil der bisher bekannten Verfahren zur Haarumformung ist, dass es nicht möglich ist, eine Umformung in relativ einfacher Weise rückgängig zu machen, d.h. von einer Frisurenform ohne aufwändige Neuerstellung zu einer anderen zu gelangen. Aus der JP 04-41416 sind Haarkosmetika bekannt, welche bestimmte lineare Polyurethane mit einer Glasübergangstemperatur Tg von 40- 90°C enthalten. Das beschriebene Verfahren zur Haarbehandlung entspricht einer Behandlung mit einem typischen Thermoplasten. Nach Auftragen der Zusammensetzung wird oberhalb von Tg dieStyling products, for example, facilitate the shaping and creation of the hairstyle as a gel, improve the status of a hairstyle as a hairspray 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 is usually done by permanent wave treatment. Here, disulfide bonds in the hair are reductively split, the hair is brought into the new shape and fixed by oxidative formation of new disulfide bonds. It is disadvantageous that the necessary chemical treatment of the hair with reducing and oxidizing agents cannot impair the structure of the hair. 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 application of the composition, the above Tg
Frisurenform erstellt und durch Abkühlen unter Tg fixiert. Bei erneutem erwärmen oberhalb Tg erweicht das Polymer und eine neue Frisur kann erstellt werden. Ein Verfahren für eine abrufbare, reversible Haarumformung wird nicht beschrieben. Die Eigenschaften der linearen Polyurethane sind für eine Anwendung zur abrufbaren Haarumformung unzureichend.Hairstyle shape created and fixed by cooling under 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 properties of linear polyurethanes are inadequate for an application for retrievable hair styling.
Die der vorliegenden Erfindung zugrunde liegende Aufgabe bestand darin, ein Verfahren und die hierfür erforderlichen Produkte für eine abrufbare, insbesondere für eine wiederholt abrufbare Haarverformung mit hohem Wiederherstellungsgrad einer programmierten Frisurenform zur Verfügung zu stellen. Eine weitere Aufgabe bestand darin, ein Verfahren zur Verfügung zu stellen, mit dem es möglich ist, eine dauerhafte Haarumformung ohne schädigenden Eingriff in die Haarstruktur zu erreichen. Eine weitere Aufgabe bestand darin, ein Verfahren zur Verfügung zu stellen, welches ermöglicht, temporäre Umformungen mehrfach in einfacher Weise rückgängig zu machen und mit hoher Genauigkeit zu einer zuvor erstellten, programmierten, permanenten Frisurenform zurückzukehren. Eine weitere Aufgabe bestand darin, ein Verfahren zur Verfügung zu stellen, welches ermöglicht, in einfacher Weise und mit hoher Genauigkeit auf äußere Einflüsse zurückzuführende Deformationen einer Frisur rückgängig zu machen und zu einer zuvor erstellten, programmierten, permanenten Frisurenform zurückzukehren.The object underlying the present invention was to provide a method and the products required for a retrievable, in particular for a repeatedly retrievable hair shaping with a high degree of restoration of a programmed hairstyle shape. Another object was to provide a method with which it is possible to achieve permanent hair styling without damaging the structure of the hair. Another task was to provide a method which makes it possible to easily undo temporary reshapings several times and to return to a previously created, programmed, permanent hairstyle shape with high accuracy. 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.
Die Aufgabe wird gelöst durch ein Verfahren zur Haarbehandlung, wobei - eine WirkstoffZusammensetzung auf das Haar aufgebracht wird, wobei die WirkstoffZusammensetzung mindestens einen Wirkstoff enthält, der ausgewählt ist aus Stoffen, welche alleine oder in Kombination mit weiteren Stoffen in der Lage sind, nach Aufbringung auf Haaren und nach Durchführung der im folgenden beschriebenen Behandlung den Haaren einen Formgedächtnis-Effekt zu verleihen; vorher, gleichzeitig oder nach dem Aufbringen der Wirkstoffzusammensetzung das Haar in eine bestimmte Form (permanente Gedächtnisform) gebracht wird und anschließend die Gedächtnisform durch Induzierung einer chemischen oder physikalischen Veränderung der aufgebrachten Wirkstoffe fixiert wird; wobei nach einer gewollten oder ungewollten Deformation der Gedächtnisform die ursprüngliche Gedächtnisform durch eine physikalische Stimulation im wesentlichen wiederherstellbar ist.The object is achieved by a method for hair treatment, wherein - An active ingredient composition is applied to the hair, the active ingredient composition containing at least one active ingredient which is selected from substances which, alone or in combination with other substances, are capable of applying to the hair after application to the hair and after the treatment described below to give a shape memory effect; 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 the memory form is then 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.
Eine besondere Ausführungsform betrifft ein Verfahren zur Haarbehandlung, wobei - eine Zusammensetzung, welche mindestens ein vernetzbaresA particular embodiment relates to a method for hair treatment, wherein - a composition which has at least one crosslinkable
Makromer, welches nach Vernetzung ein Formgedächtnispolymer bildet, auf das Haar aufgebracht wird, wobei das Makromer a) vernetzbare Bereiche enthält, die durch chemische Bindungen vernetzbar sind und b) thermoplastische Bereiche enthalten, die nicht chemisch vernetzbar sind, vorher, gleichzeitig oder anschließend das Haar in eine bestimmte (permanente) Form gebracht wird und anschließend die Form durch chemische Vernetzung des Makromers unter Ausbildung des Formgedächtnispolymers fixiert wird, wobei das Formgedächtnispolymer mindestens eine Übergangs- temperatur Ttrans aufweist. Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Aufprägung einer zweiten Frisurenform auf eine einprogrammierte, abrufbare erste Frisurenform. Hierbei wird zunächst eine durch das oben genannte Verfahren programmierte Frisur (permanente Form) auf eine Temperatur oberhalb Ttrans erwärmt. Anschließend wird das Haar in die gewünschte zweite (temporäre) Form gebracht und die zweite Form wird durch Abkühlen auf eine Temperatur unterhalb Ttrans fixiert.Macromer, which forms a shape memory polymer after crosslinking, is applied to the hair, the macromer containing a) crosslinkable regions that can be crosslinked by chemical bonds and b) thermoplastic regions that are not chemically crosslinkable, before, at the same time or subsequently, the hair is brought into a specific (permanent) shape 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.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zurAnother object of the invention is a method for
Wiederherstellung einer zuvor durch das oben genannte Verfahren einprogrammierten ersten Frisur (permanente Form) . Hierfür wird eine Frisur in einer temporären Form oder eine durch Kaltverformung deformierte Frisur auf eine Temperatur oberhalb Ttrans erwärmt.Restoration of a first hairstyle (permanent shape) previously programmed by the above procedure. For this purpose, a hairstyle in a temporary shape or a hairstyle deformed by cold deformation is heated to a temperature above Ttrans.
Formgedächtnispolymere im Sinne der Erfindung sind Polymere, aus denen sich Materialien herstellen lassen mit der Eigenschaft, dass sich ihnen eine beliebige Form (permanente Form) aufprägen läßt, in die sie sich nach einer Deformation oder nach Aufprägen einer zweiten Form (temporäre Form) spontan und ohne äußere Krafteinwirkung durch blosses Erwärmen oder durch einen anderen energetischen Stimulus zurückverwandeln. Deformation und Rückverwandlung (recovery) sind dabei mehrfach möglich. Der Grad der Erreichung der ursprünglichen, permanenten Form ist bei einem ersten Relaxationszyklus, bestehend aus Deformation und Rückverwandlung, in der Regel etwas geringer als bei nachfolgenden Zyklen, vermutlich wegen der Beseitigung von anfänglich noch vorhanden Fehlstellen, Texturen etc.. Ein besonders hoher Rückverwandlungsgrad wird dann aber bei den nachfolgendenShape memory polymers in the sense of the invention are polymers from which materials can be produced with the property that they can be imprinted with any shape (permanent shape), into which they spontaneously and after deformation or after being imprinted with a second shape (temporary shape) convert back without external force by just warming up or by another energetic stimulus. Deformation and reconversion are 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 in the following
Relaxationszyklen erreicht. Der Grad der Rückverwandlung beträgt beim ersten Relaxationszyklus vorzugsweise mindestens 30%, besonders bevorzugt mindestens 50% und bei den nachfolgenden Relaxationszyklen vorzugsweise mindestens 60%, besonders bevorzugt mindestens 80%. Er kann aber auch 90% und mehr betragen. Der Grad der Rückverwandlung kann gemessen werden wie bei üblichen curl retention Messungen durch einfache Längenmessung einer behandelten Haarlocke oder durch bekannte, geeignete Zug-Dehnungs-Experimente. Der Formgedächtnis -Effekt von Haaren ist die Eigenschaft, dass eine bestimmte Frisurenform (permanente Gedächtnisform) nach einer Deformation spontan und ohne äußere Krafteinwirkung durch blosses Erwärmen oder durch einen anderen energetischen Stimulus im wesentlichen wiederhergestellt werden kann, d.h. bei einem ersten Relaxationszyklus vorzugsweise zu mindestens 30%, besonders bevorzugt zu mindestens 50% und bei den nachfolgenden Relaxationszyklen vorzugsweise zu mindestens 60%, besonders bevorzugt zu mindestens 80% oder 90%.Relaxation cycles reached. The degree of reconversion in the first relaxation cycle is preferably at least 30%, particularly preferably at least 50% and in the subsequent relaxation cycles preferably at least 60%, particularly preferred 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 merely heating or by another energetic stimulus, i.e. preferably at least 30 in a first relaxation cycle %, particularly preferably at least 50% and in the subsequent relaxation cycles preferably at least 60%, particularly preferably at least 80% or 90%.
Zu Formgedächtnispolymeren vernetzbare Makromere bzw. Prepolymere im Sinne der Erfindung sind Polymere oder Oligomere, bei denen das Fixieren einer aufgeprägten permanenten Form dadurch erfolgt, dass einzelne Polymer- oder Oligomerstränge durch chemische Bindungen miteinander verknüpft werden. Die Vernetzung über chemische Bindungen kann über ionische oder kovalente Bindungen erfolgen. Die Vernetzungsreaktion kann eine beliebige chemische Reaktion, z.B. eine Salzbildungsreaktion, eine Kondensationreaktion, eine Additionsreaktion, eine Substitutionsreaktion oder eine radikalisch oder photochemisch induzierte Reaktion sein. Die Vernetzungsreaktion kann mittels geeigneter Katalysatoren oder Initiatoren oder katalysatorfrei erfolgen. Sie kann durch eine geeignete Energiequelle ausgelöst werden, z.B. durch elektromagnetische Strahlung, Ultraschall, Wärme oder mechanische Energie. Eine Kombination zweier oder mehrerer Startverfahren kann gegebenenfalls zur Erhöhung der Effizienz oder der Geschwindigkeit der Vernetzungsreaktion eingesetzt werden.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 linked to one another by chemical bonds. Crosslinking via chemical bonds can take place via ionic or covalent bonds. The crosslinking reaction can be any chemical reaction, e.g. 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, e.g. through 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.
Erfindungsgemäß geeignete Formgedächtnispolymere weisen mindestens eine Übergangstemperatur Ttrans auf. Hierbei kann es sich um eine Schmelztemperatur Tm oder um eine Glasübergangstemperatur Tg handeln. Oberhalb von Ttrans weist das Polymer ein niedrigeres Elastizitätsmodul auf als unterhalb von Ttrans- Das Verhältnis der Elastizitätsmodule unter- und oberhalb von Ttrans ist vorzugsweise mindestens 20. Die Übergangstemperatur Ttrans st vorzugsweise größer als Raumtemperatur (20°C) , insbesondere mindestens 30°C, besonders bevorzugt mindestens 40°C und ist diejenige Temperatur, bei deren Überschreiten die spontane Rückbildung der permanten Form aus der de ormierten oder aus der temporären Form erfolgt .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 Ttrans i above st preferably at least 20. The transition temperature Ttrans 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 de-deformed or from the temporary form takes place.
Frisur oder Frisurenform im Sinne der Erfindung ist breit zu verstehen und umfaßt beispielsweise auch den Grad der Wellung oder den Grad der Glattheit von Haaren. Eine programmierte Frisur im Sinne der Erfindung ist eine Ansammlung von Haaren, die durch vernetzte und in einer permanenten Form fixierteHairstyle 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 is networked and fixed in a permanent form
Formgedächtnispolymere eine bestimmte Form aufweisen. Wiederherstellung einer programmierten Frisur im Sinne der Erfindung bedeutet, dass sich die programmierte Frisur nach einer Deformation wieder zu vorzugsweise mindestens 60%, besonders bevorzugt mindestens 80% zurückbildet, bezogen auf die Form, die nach einem ersten Relaxationszyklus entsteht. Der Grad der Wiederherstellung kann beispielsweise durch Längenmessung einer Haarlocke oder einer Haarsträhne erfolgen.Shape memory polymers have a certain shape. Restoring a programmed hairstyle in the sense of the invention means that after a deformation the programmed hairstyle regresses again preferably 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.
Geeignete, zu Formgedächtnispolymeren chemisch vernetzbareSuitable chemically crosslinkable to shape memory polymers
Makromere oder Prepolymere sind Makromonomere, die polymerisiert oder durch einzelne chemische Bindungen vernetzt werden können. Die chemisch vernetzten Polymere werden in der WO 99/42147 auch als Thermosetpolymere bezeichnet. Die in der WO 99/42147 beschriebenen Makromere und Thermosetpolymere sind erfindungsgemäß geeignet und Bestandteil dieser Anmeldung. Weiche, thermoplastische Segmente (Schaltsegmente) mit einer Übergangstemperatur Ttrans sind durch chemische, vorzugsweise kovalente Bindungen vernetzt. Es werden also Schaltsegmente und Netzpunkte benötigt, wobei die Netzpunkte die permanente Form fixieren und die Schaltsegmente die temporäre Form. Der Formgedächtniseffekt beruht auf der Änderung der Elastizität bei über- oder unterschreiten der Ttrans- Das Verhältnis der Elastizitätsmodule unter- und oberhalb von Ttrans ist vorzugsweise mindestens 20. Je größer dieses Verhältnis, umso ausgeprägter ist der Formgedächtniseffekt. Es lassen sich vier Typen von Thermosetpolymeren mit Formgedächtniseigenschaften unterscheiden: Netzwerkpolymere, durchdringende Netzwerke, semi -durchdringende Netzwerke und gemischt durchdringende Netzwerke. Netzwerkpolymere können gebildet werden durch kovalente Verknüpfung von Macromonomeren, d.h. von Oligomeren oder Polymeren mit verknüpfbaren, reaktiven Endgruppen, vorzugsweise ethylenisch ungesättigten, radikalisch oder photochemisch reaktiven Endgruppen. Die Vernetzungsreaktion kann z.B. durch licht- oder wärmesensitive Initiatoren, durch Red-Ox-Systeme oder deren Kombinationen oder initiatorfrei, z.B. durch UV-Licht, Wärme oder mechanischen Energieeintrag gestartet werden. Durchdringende Netzwerke werden gebildet aus mindestens zwei Komponenten, die jede für sich aber nicht untereinander vernetzt sind. Gemischt durchdringende Netzwerke werden gebildet aus mindestens zwei Komponenten, wobei eine Komponente durch chemische Bindungen und eine andere Komponente durch physikalische Wechselwirkungen vernetzt ist. Semi-durchdringende Netzwerke werden gebildet aus mindestens zwei Komponenten, von denen eine chemisch vernetzbar und die andere nicht vernetzbar ist und beide Komponenten nicht durch physikalische Methoden getrennt werden können.Macromers or prepolymers are macromonomers that can be polymerized or cross-linked 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. So there are switching segments and Network points are required, with 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 exceeds or falls below. The ratio of the elasticity modules below and above Ttrans is preferably at least 20. The larger 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 networks and mixed-penetrating networks. Network polymers can be formed by covalently linking macromonomers, ie 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. Pervasive networks are formed from at least two components, each of which 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.
Grundsätzlich geeignet sind alle synthetischen oder natürlichen Oligomere und Polymere mit reaktiven End- oder Seitengruppen, welche dem vernetzten Fromgedächtnispolymer eine geeignete Übergangstemperatur Ttrans un< geeignete Elastizitätsmodule ober- und unterhalb von Ttrans verleihen und wobei die End- oder Seitengruppen entweder bereits bei der Herstellung oder anschließend durch eine Derivatisierung in einer reaktiven Form vorliegen, die eine Vernetzungsreaktion mit den o.g. Methoden zulassen. Geeignete Makromere sind z.B. solche der allgemeinen Formel Al-(X)n-A2 (I) wobei AI und A2 für reaktive, chemisch vernetzbare Gruppen stehen und -(X)n- für ein divalentes, thermoplastisches Polymer- oder Oligomersegment steht. AI und A2 sind bevorzugt Acrylat- oder Methacrylatgruppen. Das Segment (X)n steht vorzugsweise für Polyester-, Oligoester-, Polyalkylenglykol- , Oligoalkylenglykol- , Polyalkylencarbonat- und Oligoalkylencarbonatsegmente, wobei die Alkylengruppen vorzugsweise Ethylen- oder Propylengruppen sind. Geeignete Makromonomere zur Bildung von Thermosetpolymeren mit Formgedächtniseigenschaften sind Oligo- oder Poly (ε-caprolactone) , Oligo- oder Polylactide, Oligo- oder Polyalkylenglykole, z.B.Fundamentally suitable are all synthetic or natural oligomers and polymers with reactive end or side groups, which give the cross-linked form memory polymer a suitable transition temperature Ttrans and < unsuitable elasticity modules above and below Ttrans, and the end or side groups either already during production or subsequently 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 represents 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
Polyethylen- oder Polypropylenglykol oder deren Blockcopolymere, wobei die genannten Polymere oder Oligomere end- oder seitenständig mit mindestens zwei radikalisch polymerisierbaren, ethylenisch ungesättigten Gruppen, beispielsweise Acrylaten oder Methacrylaten substituiert sind.Polyethylene or polypropylene glycol or their block copolymers, the polymers or oligomers mentioned being substituted in the end or laterally with at least two free-radically polymerizable, ethylenically unsaturated groups, for example acrylates or methacrylates.
Bei den Polymersegmenten kann es sich um von natürlichen Polymeren wie z.B. Proteinen oder Polysacchariden abgeleitete Segmente handeln. Es kann sich auch um synthetische Polymerblöcke handeln. Geeignete natürliche Polymersegmente sind Proteine wie Zein, modifiziertes Zein, Casein, Gelatin, Gluten, Serum albumin oder Collagen, sowie Polysaccharide wie Alginate, Cellulosen, Dextran, Pullulan oder Polyhyaluronsäure sowie Chitin, Poly (3- hydroxyalkanoat) , insbesondere Poly (ß-hydroxybutyrat) , Poly (3- hydroxyoctanoate) oder Poly (3-hydroxyfettsäuren) . Geeignet sind auch Derivate natürlicher Polymersegmente, z.B. alkylierte, hydroxyalkylierte, hydroxylierte oder oxidierte Modifikationen. Synthetisch modifizierte natürliche Polmere sind z.B. Cellulose- derivate wie Alkylcellulosen, Hydroxyalkylcellulosen, Cellu- loseether, Celluloseester, Nitrocellulosen, Chitosan oder Chitosanderivate, die z.B. durch N- oder/und O-Alkyl- oder Hydroxyalkylsubstitution erhalten werden. Beispiele sind Methylcellulose, Ethylcellulose, Hydroxypropylcellulose, Hydroxypropylmethylcellulose , Hydroxybutylmethylcellulose , Celluloseacetat, Cellulosepropionat, Celluloseacetatbutyrat, Celluloseacetatphthalat, Carboxymethylcellulose, Cellulose- triacetat oder Cellulosesulfate Natriumsalz. Diese werden nachfolgend zusammenfassend als "Cellulosen" bezeichnet.The polymer segments can be segments derived from natural polymers such as proteins or polysaccharides. 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 (ß-hydroxybutyrate) ), Poly (3-hydroxyoctanoate) or poly (3-hydroxy fatty acids). Derivatives of natural polymer segments, for example alkylated, hydroxyalkylated, hydroxylated or oxidized modifications, are also suitable. Synthetically modified natural polymers are, for example, cellulose derivatives such as alkyl celluloses, hydroxyalkyl celluloses, cellulose loose ethers, cellulose esters, nitrocelluloses, chitosan or chitosan derivatives, which are obtained for example by N- or / and O-alkyl or hydroxyalkyl substitution. 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 collectively referred to below as "celluloses".
Geeignete synthetische Polymerblöcke sind Polyphosphazene, Poly(vinyl alcohole), Polyamide, Polyesteramide, Polyaminosäuren, Polyanhydride , Polycarbonate, Poly (lactid-co-glycolide) , Polyacrylate, Polyalkylene, Polyacrylamide, Polyalkylenglycole, Polyalkylenoxide, Polyalkylenterephthalate, Polyorthoester, Polyvinylether, Polyvinylester, Polyvinylhalogenide, Polyvinylpyrrolidon, Polyester, Polylactide, Polyglycolide, Polysiloxane, Polyurethane sowie deren Copolymere. Beispiele geeigneter Polyacrylate sind Poly (methylmethacrylat) , Poly (ethylmethacrylat) , Poly (butylmethacrylat) ,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 of suitable polyacrylates are poly (methyl methacrylate), poly (ethyl methacrylate), poly (butyl methacrylate),
Poly (isobutylmethacrylat) , Poly (hexylmethacrylat) , Poly (isodecylmethacrylat) , Poly (laurylmethacrylat) , Poly (phenylmethacrylat) , Poly (methylacrylat) , Poly (isopropylacrylat) , Poly (isobutylacrylat) oder Poly- (octadecylacrylat) . Geeignete synthethische, leicht biologisch abbaubare Polymersegmente sind Polyhydroxysauren wie Polylactide, Polyglycolide und deren Copolymere, Poly (ethylenterephthalat) ,- Poly (hydroxybutansäure) ,- Poly (hydroxyvaleriansäure) ; Poly[lactid- co- (ε-caprolacton) ] ; Poly [glycolid-co- (ε-caprolacton) ] ; Polycarbonate, Poly (aminosäuren) ; Poly (hydroxyalkanoate) ,- Polyanhydride; Polyorthoester sowie deren Mischungen und Copolymere. Beispiele schlechter biologisch abbaubarer Polymersegmente sind Poly (methacrylsäure) , Poly (acrylsäure) , Polyamide, Polyethylen, Polypropylen, Polystyrol, Polyvinylchlorid, Polyvinylphenol sowie deren Mischungen und Copolymere .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, Polyvinyl chloride, polyvinylphenol and their mixtures and copolymers.
In einer besonders bevorzugten Ausführungsform enthält die Zusammensetzung eine Mischung aus (A) Makromeren die mit mindestens zwei reaktiven, vernetzbaren Gruppen substituiert sind und (B) Makromeren, die mit nur einer reaktiven Gruppe substituiert sind. Geeignete zusätzliche Makromere sind z.B. solche der allgemeinen Formel R-(X')n-A3 (II) wobei R für einen monovalenten organischen Rest, A3 für eine reaktive, chemisch vernetzbare Gruppe und -(X')n- für ein divalentes, thermoplastisches Polymer- oder Oligomersegment steht. A3 ist vorzugsweise eine Acrylat- oder Methacrylatgruppe . Das Segment (X')n steht vorzugsweise für Polyalkylenglykole, deren Monoalkylether sowie deren Blockcopolymere, wobei die Alkylengruppen vorzugsweise Ethylen- oder Propylengruppen sind und die Alkylgruppen vorzugsweise 1 bis 30 C-Atome aufweisen. Besonders bevorzugt sind Mischungen aus (A) endständig an beiden Enden mit Acryl- oder Methacrylsäure verestertenIn 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, for example, those of the general formula R- (X ') n -A3 (II) where R for a monovalent organic radical, A3 for a reactive, chemically crosslinkable group and - (X') n- for a divalent, thermoplastic Polymer or oligomer segment stands. 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
Polyalkylenglykolen oder Polycaprolactonen und (B) endständig an einem Ende mit Acryl- oder Methacrylsäure veresterten Polyalkylenglykol-monoalkylethern, wobei die Alkylengruppen vorzugseise Ethylen- oder Propylengruppen und die Alkylgruppen vorzugsweise Cl- bis C30-Alkylgruppen sind. Als Komponente (A) sind z.B. geeignet: Poly (ε-caprolacton) -dimethacrylat, Poly(DL- lactid) -dimethacrylat, Poly (L-lactid-co-glycolid) -dimethacrylat, Poly (ethylenglykol) dimethacrylat, Poly (propylen- glykol) dimethacrylat, PEG-block-PPG-block-PEG-dimethacrylat, Poly (ethylenadipat) -dimethacrylat, Hexamethylencarbonat-dimethacrylat. Als Komponente (B) sind z.B. geeignet: Poly- (ethylenglykol)monoacrylat, Poly (propylenglykol) monoacrylat und deren Monoalkylether. Eine weitere besondere Ausfuhrungsform betrifft ein Verfahren zurPolyalkylene 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. The following are suitable as component (A): 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. Suitable as component (B) are, for example: poly (ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate and their monoalkyl ether. Another special embodiment relates to a method for
Haarbehandlung, wobeiHair treatment, being
- eine Zusammensetzung, welche mindestens ein Form- gedächtnispolymer enthält, auf das Haar aufgebracht wird, wobei das Formgedächtnispolymer mindestens zwei Übergangstemperaturena composition which contains at least one shape memory polymer is applied to the hair, the shape memory polymer having at least two transition temperatures
Ttrans un& τ'trans aufweist und a) mindestens ein durch physikalische Wechselwirkung vernetzbares hartes Segment mit einer ersten Übergangstemperatur T'trans» die oberhalb Raumtemperatur, vorzugsweise mehr als 10°C oberhalb Raumtemperatur liegt, und b) mindestens ein weiches Segment mit einer zweitenTtrans un & τ 'trans and a) at least one hard segment which can be crosslinked by physical interaction with 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
Übergangstemperatur T rans» welche unterhalb von T'trans» vorzugsweise um mindestens 10 °C unterhalb von T'trans liegt, aufweist, - vorher, gleichzeitig oder anschließend das Haar in eine bestimmte (permanente) Form gebracht wird und anschließend die Form durch physikalische Vernetzung der Formgedächtnispolymere fixiert wird. Die Formgebung der Haare erfolgt zweckmäßigerweise unter Erwärmung auf eine Temperatur von mindestens T'trans und die Haarform wird durch Abkühlung auf eine Temperatur unterhalb T'trans fixiert. Raumtemperatur bedeutet in der Regel Umgebungstemperatur, vorzugsweise mindestens 20°C, bei wärmerem Klima vorzugsweise mindestens 25°C. Das Aufbringen der Zusammensetzung auf das Haar kann auf verschiedenene Weisen erfolgen, z.B. direkt durchTransition temperature T rans », which is below T'trans», preferably at least 10 ° C below T'trans, has - before, at the same time or subsequently, the hair is brought into a specific (permanent) shape and then the shape by physical crosslinking the shape memory polymer is fixed. The hair is expediently shaped with heating to a temperature of at least T'trans and the hair shape is fixed by cooling to a temperature below T'trans. 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
Versprühen oder indirekt durch Aufbringen zunächst auf die Hand oder auf ein geeignetes Hilfsmittel wie z .B. Kamm, Bürste etc. und anschließendem Verteilen im bzw. auf dem Haar. Die Konsistenz der Zusammensetzung kann beispielsweise diejenige sein einer Lösung, Dispersion, Lotion, verdickten Lotion, Gel, Schaum, einer halbfesten Masse, cremeartig oder wachsartig.Spray or indirectly by applying it first to the hand or to a suitable device such as. 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.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Aufprägung einer zweiten Frisurenform auf eine einprogrammierte, abrufbare erste Frisurenform. Hierbei wird zunächst eine durch das oben genannte Verfahren programmierte Frisur (permanente Form) auf eine Temperatur zwischen T'trans un(3 Ttrans erwärmt. Anschließend wird das Haar in die gewünschte zweite (temporäre) Form gebracht und die zweite Form wird durch Abkühlen auf eine Temperatur unterhalb Ttrans fixiert.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 between T'trans un ( 3 Ttrans). The hair is then brought into the desired second (temporary) shape and the second shape is cooled to a Fixed temperature below Ttrans.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Wiederherstellung einer zuvor durch das oben genannte Verfahren einprogrammierten ersten Frisur (permanente Form) . Hierfür wird eine Frisur in einer temporären Form oder eine durch Kaltverformung deformierte Frisur auf eine Temperatur oberhalb Ttrans erwärmt wird. Die permanente Form bildet sich dabei spontan und selbsttätig zurück. Unter Kaltverformung einer Frisur ist eine Frisurenänderung bei Umgebungstemperatur, ohne Zuführung von zusätzlicher Wärme durch einen Haartrockner oder ähnliche Geräte zu verstehen. Die Verformung kann dabei mechanisch verursacht sein, z.B. durch bloßes Aushängen der Locken unter Schwerkrafteinwirkung, durch Kämmen oder Bürsten der Haare, durch Wind oder Feuchtigkeit, durch mechanische Einflüsse während des Schlafens oder Liegens etc ..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, e.g. by simply unhooking the curls under the influence of gravity, by combing or brushing the hair, by wind or moisture, by mechanical influences while sleeping or lying down etc.
Die Erfindung betrifft außerdem ein Verfahren zur Umprogrammierung einer zuvor nach dem oben genannten Verfahren programmierten permanenten Frisurenform in eine andere, neue permanente Form.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.
Hierzu wird die ursprüngliche Frisur auf eine Temperatur oberhalb T'trans erwärmt und das Haar in eine neue Form gebracht. Anschließend wird die neue Form durch Abkühlen auf eine Temperatur unterhalb T'trans fixiert.For this purpose, the original hairstyle is heated to a temperature above T'trans and the hair is brought into a new shape. The new shape is then fixed by cooling to a temperature below T'trans.
Physikalisch vernetzbare Formgedächtnispolymere im Sinne der Erfindung sind Polymere, bei denen das Fixieren der aufgeprägten permanenten Form durch Vernetzung aufgrund von physikalischen Wechselwirkungen erfolgt. Eine Vernetzung durch physikalische Wechselwirkungen kann dadurch erfolgen, dass sich bestimmte Segmente der Polymerketten zu kristallinen Bereichen zusammenlagern. Bei den physikalischen Wechselwirkungen kann es sich um Charge transfer Komplexe, um Wasserstoffbrückenbindungen, um dipolare oder hydrophobe Wechselwirkungen, um van der Waals- Wechselwirkungen oder um ionische Wechselwirkungen von Polyelektrolytsegmenten handeln. Die Wechselwirkungen können zwischen verschiedenen Segmenten innerhalb eines Polymerstranges (intramolekular) und/oder zwischen verschiedenen Polymersträngen (intermolekular) erfolgen. Die Ausbildung der Wechselwirkungen kann beispielsweise durch Abkühlen (insbesondere im Falle von Kristallisationen) und/oder durch Trocknen, d.h. durch Entfernen von Lösungsmitteln ausgelöst werden.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. Networking 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 formation of the interactions can be triggered, for example, by cooling (in particular in the case of crystallizations) and / or by drying, ie by removing solvents.
Erfindungsgemäß geeignete physikalisch vernetzbare Formgedächtnispolymere weisen mindestens zwei Übergangstemperaturen Ttrans und T'trans auf. Bei beiden Übergangstemperaturen kann es sich z.B. um Schmelztemperaturen Tm oder um Glasübergangstemperaturen Tg handeln. Oberhalb von Ttrans weist das Polymer ein niedrigeres Elastizitätsmodul auf als unterhalb von Ttrans • Das Verhältnis der Elastizitätsmodule unter- und oberhalb von Ttrans st vorzugsweise mindestens 10, besonders bevorzugt mindestens 20. Die untere Übergangstemperatur Ttrans ist vorzugsweise größer als Raumtemperatur (20°C) , insbesondere mindestens 30°C, besonders bevorzugt mindestens 35°C oder mindestens 40°C und ist diejenige Temperatur, bei deren Überschreiten die spontane Rückbildung der permanten Form aus der deformierten oder aus der temporären Form erfolgt . Ttrans liegt vorzugsweise soweit oberhalb von gewöhnlich zu erwartenden Umgebungstemperaturen, dass bei Umgebungstemperatur keine signifikante, unbeabsichtigte, thermisch induzierte Verformung der temporären Frisurenform auftritt. Geeignete Bereiche für Ttrans sind z.B. von 25 bis 100°C, von 30 bis 75°C, von von 35 bis 70°C oder von 40 bis 60°C. Die obere Übergangstemperatur T'trans liegt über Ttrans und ist diejenige Temperatur, oberhalb der die Aufprägung der permanenten Form oder die Umprägung einer permanenten Form in eine neue permanente Form erfolgt und durch deren Unterschreiten die permanente Form fixiert wird. T'trans liegt vorzugsweise soweit oberhalb von Ttrans» dass bei Erwärmung der Frisur auf eine Temperatur oberhalb Ttrans zur Wiederherstellung der permanenten Frisurenform oder zur Neuerstellung einer temporären Frisurenform unter Beibehaltung der permanenten Frisurenform keine signifikante, unbeabsichtigte, thermisch induzierte Verformung der permanenten Frisurenform auftritt.Physically crosslinkable shape memory polymers suitable according to the invention have at least two transition temperatures Ttrans and d T'trans. Both transition temperatures can be, for example, melting temperatures T m or glass transition temperatures Tg. Above T trans, the polymer has a lower modulus of elasticity than below Ttrans • lower the ratio of the elasticity modules and Ttrans above st preferably at least 10, more preferably at least 20. The lower transition temperature Ttrans i st 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'trans is via Ttrans and 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 Ttrans 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.
Vorzugsweise liegt T'trans mindestens 10°C, besonders bevorzugt mindestens 20°c oder mindestens 30°C oberhalb Ttrans- D Differenz zwischen T'trans und Ttrans kann beispielsweise von 10 bis 80°C, von 20 bis 70°C oder von 30 bis 60°C betragen. Geeignete Bereiche für T'trans sind z.B. von 40 bis 150°C, von 50 bis 100°C oder von 70 bis 95°C.T'trans is preferably at least 10 ° C, particularly preferably at least 20 ° C or at least 30 ° C above Ttrans-D difference between T'trans and Ttrans can be, for example, from 10 to 80 ° C, from 20 to 70 ° C or from 30 to 60 ° C. Suitable ranges for T'trans are, for example, from 40 to 150 ° C, from 50 to 100 ° C or from 70 to 95 ° C.
Geeignete physikalisch vernetzte Formgedächtnispolymere sind Polymere, welche aus mindestens einem harten Segment und mindestens einem weichen Segment bestehen. Das harte Segment weist physikalische Vernetzungen auf und hat eine Übergangstemperatur T'trans °Lie oberhalb Raumtemperatur, vorzugsweise mehr als 10°C oberhalb 20°C liegt. Das weiche Segment hat eine Übergangstemperatur Ttra s» welche unterhalb von T'trans» vorzugsweise um mindestens 10°C unterhalb von T'trans liegt. Die Polymersegmente sind vorzugsweise Oligomere, insbesondere lineare Kettenmoleküle mit einem Molekulargewicht von beispielsweise 400 bis 30000, vorzugsweise 1000 bis 20000 oder 1500 bis 15000. Es kann sich um lineare Di-, Tri, Tetra- oder Multiblockcopolymere, um verzweigte, dendritische oder gepfropfte Copolymere handeln.Suitable physically cross-linked shape memory polymers are polymers which consist of at least one hard segment and at least one soft segment. The hard segment has physical cross-links and has a transition temperature T'trans ° Lie above room temperature, preferably more than 10 ° C above 20 ° C. The soft segment has a transition temperature Ttra s »which is below T'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 ,
Vorzugsweise handelt es sich nicht um lineare Polyetherurethane, die Bis (2-hydroxy-ethyl) -hydrochinon enthalten. Das Molekulargewicht der Polymere kann beispielsweise von 30000 bis 1000000, vorzugsweise von 50000 bis 700000 oder von 70000 bis 400000 betragen. Geeignete physikalisch vernetzte Formgedächtnispolymere sind in der WO 99/42147 beschrieben und werden dort als thermoplastische Polymere bezeichnet . Die in der WO 99/42147 beschriebenen thermoplastischen Polymere sowie die dort beschriebenen Herstellungsmethoden sind erfindungsgemäß geeignet und Bestandteil dieser Anmeldung. Sie weisen einenThey 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
Kristallinitätsgrad von vorzugsweise 3 bis 80%, besonders bevorzugt von 3 bis 60% auf. Das Verhältnis der Elastizitätsmodule unter- und oberhalb von Ttrans is vorzugsweise mindestens 10, besonders bevorzugt mindestens 20. Bei den Polymersegmenten kann es sich um von natürlichen Polymeren wie z.B. Proteinen oder Polysacchariden abgeleitete Segmente handeln. Es kann sich auch um synthetische Polymerblöcke handeln. Geeignete natürliche oder synthetische Polymersegmente sind die gleichen wie die oben für die vernetzbaren Makromere genannten.Degree of crystallinity of preferably 3 to 80%, particularly preferably 3 to 60%. The ratio of the elastic modulus below and above 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.
Geeignete Formgedächtnispolymere sind insbesondere Multiblock- Copolymere, welche mindestens eine erste Art von Blöcken und mindestens eine davon verschiedene zweite Art von Blöcken aufweisen, wobei die Blöcke bewirken, dass das Multiblock- Copolymer zwei verschiedene Übergangstemperaturen aufweist. Geeignete Multiblock-Copolymere sind insbesondere solche, die hergestellt sind aus mindestens zwei verschiedenen Macrodiolen und mindestens einem Diisocyanat. Macrodiole sind Oligomere oder Polymere mit mindestens zwei freien Hydroxygruppen . Oligomere bestehen in der Regel aus mindestens zwei, vorzugsweise mindestens drei, insbesondere 4 bis 20, 5 bis 15 oder 6 bis 10 Monomeren. Die Macrodiole können die allgemeine Formel HO-A-OH aufweisen, wobei A eine divalente, oligomere oder polymere Gruppe bedeutet, vorzugsweise Polyester oder Oligoester. Das Diisocyanat kann die allgemeine Formel OCN-B-NCO aufweisen, wobei B für eine divalente organische Gruppe steht, vorzugsweise für eine Alkylen- oder Arylengruppe , die mit weiteren Substituenten substituiert sein kann. Die Alkylengruppe kann linear, verzweigt oder cyclisch sein und hat vorzugsweise 1 bis 30 C-Atome, besonders bevorzugt 2 bis 20 oder 5 bis 15 C-Atome.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, 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.
Besonders bevorzugte Formgedächtnispolymere sind die in der WO 99/42147 beschriebenen Copolyesterurethane, insbesondere den Reaktionsprodukten aus (a) zwei verschiedenen Macrodiolen, ausgewählt aus α,ω-Dihydroxy-polyestern, α,ω-Dihydroxy- oligoestern, α,ω-Dihydroxy-polylactonen und α,ω-Dihydroxy- oligolactonen und (b) mindestens einem Diisocyanat, bevorzugt Trimethylhexan-1, 6-diisocyanat . Besonders bevorzugt sindParticularly 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
Makrodiole aus Poly (para-dioxanon) (PDX) , Poly (pentadecalacton) (PDL) , Poly (ε-caprolacton) (PCL), Poly (L-lactid-co-glycolid) (PLGA) . Die Molmassen der Makrodiole liegen bevorzugt im Bereich von 400 bis 30000, vorzugsweise 1000 bis 20000 oder 1500 bis 15000. Die Molmassen der resultiernden Multiblock-Copolymere betragen bevorzugt Mw = von 30000 bis 1000000, besonders bevorzugt von 50000 bis 700000 oder von 70000 bis 400000 g/mol, bestimmbar durch GPC . Die Polydispersitäten liegen vorzugsweise im Bereich von 1,7 - 2,0.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 w = 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.
Eine weitere besondere Ausführungsform betrifft ein Verfahren zur Haarbehandlung unter Verwendung einer WirkstoffZusammensetzung in der mindestens zwei Wirkstoffe enthalten sind, die einzeln keine oder nur schwache Formgedächtniseigenschaften aufweisen und die bei gemeinsamer Anwendung gemäß den onben genannten Verfahren Haaren einen synergistisch gesteigerten Formgedächtnis-Effekt verleihen.A further particular embodiment relates to a method for hair treatment using an active ingredient composition which contains at least two active ingredients which individually have no or only weak shape memory properties and which, when used together in accordance with the abovementioned methods, give hair a synergistically increased shape memory effect.
Erfindungsgemäße Zusammensetzungen für die Haarbehandlung enthalten mindestens einen, einen Formgedächtniseffekt von Haaren bewirkenden Wirkstoff in einer Menge von vorzugsweise 0,01 bis 25 Gew.%, besonders bevorzugt von 0,1 bis 15 Gew.% in einem geeigneten Medium. Die Zusammensetzung kann u.a. als Lösung, Dispersion, Emulsion, Suspension oder Latex vorliegen. Das flüssige, gelförmige, halbfeste oder feste Medium ist dabei im wesentlichen kosmetisch akzeptabel und physiologisch unbedenklich.Compositions according to the invention for hair treatment contain at least one active ingredient which brings about a shape memory effect on hair in an amount of preferably from 0.01 to 25% by weight, particularly preferably from 0.1 to 15% by weight, in a suitable medium. The composition can be in the form of a solution, dispersion, emulsion, suspension or latex. The liquid, gel-like, semi-solid or solid medium is essentially cosmetically acceptable and physiologically harmless.
Die erfindungsgemäße Zusammensetzung liegt im allgemeinen als Lösung oder Dispersion in einem geeigneten Lösungsmittel vor. Besonders bevorzugt sind wäßrige, alkoholische oder wäßrigalkoholische Lösungsmittel. Geeignete Lösungsmittel sind z.B. aliphatische Cl- bis C4-Alkohole oder ein Gemisch von Wasser mit einem dieser Alkohole. Es können jedoch auch andere organische Lösungsmittel eingesetzt werden, wobei insbesondere unverzweigte oder verzweigte Kohlenwasserstoffe wie Pentan, Hexan, Isopentan, cyklische Kohlenwasserstoffe wie Cyclopentan und Cyclohexan, organische lineare oder cyclische Ether, z.B. Tetrahydrofuran (THF) oder flüssige organische Ester, z.B. Ethylacetat zu nennen sind. Weiterhin sind auch Lösungsmittel auf Silikonbasis geeignet, insbesonders Silikonöle auf Basis linearer oder cyclischer Polydimethylsiloxane (Dimethicone oder Cyclomethicone) . Die Lösungsmittel liegen bevorzugt in einer Menge von 0,5 bis 99 Gew.%, besonders bevorzugt in einer Menge von 40 bis 90 Gew.% vor.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 e.g. aliphatic Cl to C4 alcohols or a mixture of water with one of these alcohols. However, other organic solvents can also be used, in particular unbranched or branched hydrocarbons such as pentane, hexane, isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane, organic linear or cyclic ethers, e.g. Tetrahydrofuran (THF) or liquid organic esters, e.g. Ethyl acetate should be mentioned. Furthermore, silicone-based solvents are also suitable, in particular silicone oils based on linear or cyclic polydimethylsiloxanes (dimethicone or cyclomethicone). The solvents are preferably present in an amount of 0.5 to 99% by weight, particularly preferably in an amount of 40 to 90% by weight.
Erfindungsgemäße Zusammensetzungen können zusätzlich 0,01 bis 25 Gew.% mindestens eines haarpflegenden, haarfestigenden und/oder haarfärbenden Wirkstoffes enthalten.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.
Haarfestigende Wirkstoffe sind insbesondere die bekannten, herkömmlichen filmbildenden und haarfestigenden Polymeren. Das filmbildende und haarfestigende Polymer kann synthetischen oder natürlichen Ursprungs sein und nichtionischen, kationischen, anionischen oder amphoteren Charakter haben. Ein derartiger Polymerzusatz, der in Mengen von 0,01 bis 25 Gew.%, vorzugsweise 0,1 bis 20 Gew.%, besonders bevorzugt von 0,5 bis 15 Gew.% enthalten sein kann, kann auch aus einem Gemisch von mehreren Polymerern bestehen und durch den Zusatz von weiteren Polymeren mit verdickender Wirkung in seinen haarfestigenden Eigenschaften modifiziert werden. Unter filmbildenden, haarfestigenden Polymeren werden erfindungsgemäß solche Polymere verstanden, die bei Anwendung in 0,01 bis 5%-iger wäßriger, alkoholischer oder wäßrigalkoholischer Lösung in der Lage sind, auf dem Haar einen Polymerfilm abzuscheiden und auf diese Weise das Haar zu festigen.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 by the addition of other polymers with thickening effect in its hair-setting properties be modified. According to the invention, film-forming, hair-fixing polymers are understood to mean those polymers which, when used in 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.
Als geeignete synthetische, nichtionische, filmbildende, haarfestigende Polymere können in dem erfindungsgemäßen Haarbehandlungsmittel Homopolymere des Vinylpyrrolidons, Homopolymere des N-Vinylformamids, Copolymerisate aus Vinylpyrrolidon und Vinylacetat, Terpolymere aus Vinylpyrrolidon, Vinylacetat und Vinylpropionat , Polyacrylamide, Polyvinylalkohole, oder Polyethylenglykole mit einem Molekulargewicht von 800 bis 20.000 g/mol eingesetzt werden. Unter den geeigneten synthetischen, filmbildenden anionischen Polymeren sind zu nennenSuitable 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, or polyethyleneglycols, polyvinyl alcohols up to 20,000 g / mol can be used. Suitable synthetic, film-forming anionic polymers should be mentioned
Crotonsäure/Vinylacetat Copolymere und Terpolymere aus Acrylsäure, Ethylacrylat und N-t-Butylacrylamid. Natürliche filmbildende Polymere oder daraus durch chemische Umwandlung hergestellte Polymere können in dem erfindungsgemäßen Haarbehandlungsmittel ebenfalls eingesetzt werden. Bewährt haben sich niedermolekulares Chitosan mit einem Molekulargewicht von 30.000 bis 70.000 g/mol oder hochmolekulares Chitosan, organolösliche Derivate des Chitosans, Gemische aus Oligo-, Mono- und Disacchariden, chinesisches Balsamharz, Cellulosederivate wie Hydroxypropylcellulose mit einem Molekulargewicht von 30.000 bis 50.000 g/mol, oder Schellack in neutralisierter oder unneutralisierter Form. Auch amphotere Polymere können in dem erfindungsgemäßen Haarbehandlungsmittel eingesetzt werden. Geeignet sind z. B. Copolymere aus Octylacrylamid, t- Butylaminoethylmethacrylat sowie zwei oder mehr Monomeren aus der Gruppe Acrylsäure, Methacrylsäure und deren einfachen Estern. Unter den kationischen Polymeren, die erfindungsgemäß eingesetzt werden können, sind Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats- und - methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon/Dimethylaminomethacrylat Copolymere zu nennen. Weitere kationische Polymere sind beispielsweise das Copolymerisat des Vinylpyrrolidons mit Vinylimidazoliummethochlorid, das Terpolymer aus Dimethyldiallylammoniumchlorid, Natriumacrylat und Acrylamid, das Terpolymer aus Vinylpyrrolidon, Dimethyl- aminoethylmethacrylat und Vinylcarprolactam, das quaternierte Ammoniumsalz, hergestellt aus Hydroxyethylcellulose und einem mit Trimethylammonium substituierten Epoxid, das Vinylpyrro- lidon/Methacrylamidopropyltrimethylammoniumchlorid Copolymer und diquaternäre Polydimethylsiloxane .Crotonic acid / vinyl acetate copolymers and terpolymers made from acrylic acid, ethyl acrylate and Nt-butylacrylamide. Natural film-forming polymers or polymers made therefrom by chemical conversion can also be used in the hair treatment composition according to the invention. Low molecular weight chitosan with a molecular weight of 30,000 to 70,000 g / mol or high molecular weight chitosan, organo-soluble derivatives of chitosan, mixtures of oligo-, mono- and disaccharides, Chinese balsam resin, cellulose derivatives such as hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol have proven successful , 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. Among the cationic polymers that can be used according to the invention are copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone / dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Other cationic polymers include the copolymer of vinyl pyrrolidone with vinyl, the terpolymer of dimethyldiallyl 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, vinyl pyrrolidone / Methacrylamidopropyltrimethylammonium chloride copolymer and diquaternary polydimethylsiloxanes.
Die Konsistenz des erfindungsgemäßen Haarbehandlungsmittels kann durch den Zusatz von Verdickern erhöht werden. Hierfür sind beispielsweise Homopolymere der Acrylsäure mit einemThe consistency of the hair treatment composition according to the invention can be increased by adding thickeners. Homopolymers of acrylic acid with a
Molekulargewicht von 2.000.000 bis 6.000.000 g/mol geeignet. Auch Copolymere aus Acrylsäure und Acrylamid (Natriumsalz) mit einem Molekulargewicht von 2.000.000 bis 6.000.000 g/mol, Sclerotium Gum und Copolymere der Acrylsäure und der Methacrylsäure sind geeignet .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 also suitable.
Ein erfindungsgemäßes kosmetisches Mittel kann in verschiedenen Applikationsformen Anwendung finden, wie beispielsweise in Form einer Lotion, einer Sprühlotion, einer Creme, eines Gels, eines Gelschaums, eines Aerosolsprays, eines Nonaerosolsprays, eines Aerosolschaums, eines Nonaerosolschaums, einer O/W- oder W/0- Emulsion, einer Mikroemulsion oder eines Haarwachses .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 / 0- emulsion, a microemulsion or a hair wax.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form eines Aerosolsprays vorliegt, so enthält es zusätzlich 15 bis 85 Gew.%, bevorzugt 25 bis 75 Gew.% eines Treibmittels und wird in einem Druckbehälter mit Sprühkopf abgefüllt . Als Treibmittel sind niedere Alkane, wie z.B. n-Butan, Isobutan und Propan, oder auch deren Gemische sowie Dimethylether oder Fluorkohlenwasserstoffe wie F 152a (1 , 1-Difluorethan) oder F 134 (Tetrafluorethan) sowie ferner bei den in Betracht kommenden Drücken gasförmig vorliegende Treibmittel, wie N2 , N2O und C02 sowie Gemische der vorstehend genannten Treibmittel geeignet.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, such as, for example, n-butane, isobutane and propane, or else mixtures thereof, and also dimethyl ether or fluorocarbons are used as blowing agents such as F 152a (1, 1-difluoroethane) or F 134 (tetrafluoroethane) and, furthermore, gaseous blowing agents such as N 2 , N2O and C0 2 and mixtures of the abovementioned blowing agents are suitable at the pressures under consideration.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form eines versprühbaren Non-Aerosol Haarsprays vorliegt, so wird es mit Hilfe einer geeigneten mechanisch betriebenen Sprühvorrichtung versprüht. Unter mechanischen Sprühvorrichtungen sind solche Vorrichtungen zu verstehen, welche das Versprühen einerIf 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 spray one
Zusammensetzung ohne Verwendung eines Treibmittels ermöglichen. Als geeignete mechanische Sprühvorrichtung kann beispielsweise eine Sprühpumpe oder ein mit einem Sprühventil versehener elastischer Behälter, in dem das erfindungsgemäße kosmetische Mittel unter Druck abgefüllt wird, wobei sich der elastischeAllow composition without using a blowing agent. 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 one
Behälter ausdehnt und aus dem das Mittel infolge der Kontraktion des elastischen Behälters bei Öffnen des Sprühventils kontinuierlich abgegeben wird, verwendet werden.Expands container and from which the agent is continuously released due to the contraction of the elastic container when the spray valve is opened.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form eines Haarschaumes (Mousse) vorliegt, so enthält es mindestens eine übliche, hierfür bekannte schaumgebende Substanz. Das Mittel wird mit oder ohne Hilfe von Treibgasen oder chemischen Treibmitteln verschäumt und als Schaum in das Haar eingearbeitet und ohne Ausspülen im Haar belassen. Ein erfindungsgemäßes Produkt weist als zusätzliche Komponente eine Vorrichtung zum Verschäumen der Zusammensetzung auf . Unter Vorrichtungen zum Verschäumen sind solche Vorrichtungen zu verstehen, welche das Verschäumen einer Flüssigkeit mit oder ohne Verwendung eines Treibmittels ermöglichen. Als geeignete mechanische Schäumvorrichtung kann beispielsweise ein handelsüblicher Pumpschäumer oder ein Aeroso1schaumkopf verwendet werden . Wenn das erfindungsgemäße Haarbehandlungsmittel in Form eines Haargels vorliegt, so enthält es zusätzlich mindestens eine gelbildende Substanz in einer Menge von vorzugsweise 0,05 bis 10, besonders bevorzugt von 0,1 bis 2 Gew.%. Die Viskosität des Gels beträgt vorzugsweise von 100 bis 50.000 mm /s , besonders bevorzugt von 1.000 bis 15.000 mm /s bei 25°C, gemessen als dynamische Viskositätsmessung mit einem Bohlin Rheometer CS, Messkörper C25 bei einer Schergeschwindigkeit von 50 s .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 can be used, for example, 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.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form einesIf the hair treatment composition according to the invention in the form of a
Haarwachses vorliegt, so enthält es zusätzlich wasserunlösliche Fett- oder Wachsstoffe oder Stoffe, die der Zusammensetzung eine wachsähnliche Konsistenz verleihen, in einer Menge von vorzugsweise 0,5 bis 30 Gew.%. Geeignete wasserunlösliche Stoffe sind beispielsweise Emulgatoren mit einem HLB-Wert unterhalb von 7, Silikonöle, Silikonwachse, Wachse (z.B. Wachsalkohole, Wachssäuren, Wachsester, sowie insbesondere natürliche Wachse wie Bienenwachs, Carnaubawachs , etc.), Fettalkohole, Fettsäuren, Fettsäureester oder hochmolekulare Polyethylenglykole mit einem Molekulargewicht von 800 bis 20.000, vorzugsweise von 2.000 bis 10.000 g/mol.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 a molecular weight of 800 to 20,000, preferably from 2,000 to 10,000 g / mol.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form einer Haarlotion vorliegt, so liegt es als im wesentlichen nicht-viskose oder gering viskose, fließfähige Lösung, Dispersion oder Emulsion mit einem Gehalt an mindestens 10 Gew.%, vorzugsweise 20 bis 95 Gew.% eines kosmetisch verträglichen Alkohols vor. Als Alkohole können insbesondere die für kosmetische Zwecke üblicherweise verwendeten niederen Cl- bis C4-Alkohole wie z.B. Ethanol und Isopropanol verwendet werden.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.
Wenn das erfindungsgemäße Haarbehandlungsmittel in Form einer Haarcreme vorliegt, so liegt es vorzugsweise als Emulsion vor und enthält entweder zusätzlich viskositätsgebende Inhaltsstoffe in einer Menge von 0,1 bis 10 Gew.% oder die erforderliche Viskosität und cremige Konsistenz wird durch Micellbildung mit Hilfe von geeigneten Emulgatoren, Fettsäuren, Fettalkoholen, Wachsen etc. in üblicher Weise aufgebaut.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 a quantity of 0.1 to 10% by weight or the required viscosity and creamy consistency is built up in a conventional manner by micelle formation with the aid of suitable emulsifiers, fatty acids, fatty alcohols, waxes etc.
In einer bevorzugten Ausführungsform ist das erfindungsgemäße Mittel in der Lage, gleizeitig sowohl die Aufprägung einer abrufbaren Frisur als auch eine Haarfärbung zu ermöglichen. Das Mittel ist dann als färbendes Haarbehandlungsmittel wie z.B. als Farbfestiger, Färbecreme, Färbeschaum etc. formuliert. Es enthält dann mindestens einen färbenden Stoff. Hierbei kann es sich um organische Farbstoffe, insbesondere um sogenannte direktziehnde Farbstoffe oder auch um anorganische Pigmente handeln.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 used as a coloring hair treatment agent, e.g. Formulated 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.
Die Gesamtmenge an Farbstoffen beträgt in dem erfindungsgemäßen Mittel etwa 0,01 bis 7 Gew.%, vorzugsweise etwa 0,2 bis 4 Gew.%. Für das erfindungsgemäße Mittel geeignete direktziehende Farbstoffe sind beispielsweise Triphenylmethanfarbstoffe, aromatische Nitrofarbstoffe, Azofarbstoffe, Chinonfarbstoffe, kationische oder anionische Farbstoffe. Geeignet sind: Nitrofarbstoffe (blau) :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 are: Nitro dyes (blue):
1,4-Bis [ (2-hydroxyethyl) amino] -2-nitrobenzol, 1- (2-Hydroxy- ethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] -benzol (HC Blue No. 2) , l-Amino-3-methyl-4- [ (2-hydroxyethyl) amino] -6-nitrobenzol (HC Violet No. 1), 4- [Ethyl- (2-hydroxyethyl) amino] -1- [ (2- hydroxyethyl) amino] -2-nitrobenzol-hydrochlorid (HC Blue No. 12), 4- [Di (2-hydroxyethyl) amino] -1- [ (2-methoxyethyl) amino] -2- nitrobenzol (HC Blue No. 11), 1- [ (2, 3-Dihydroxypropyl) amino] -4- [methyl- (2-hydroxyethyl) amino] -2-nitrobenzol (HC Blue No. 10), 1- [ (2, 3-Dihydroxypropyl) amino] -4- [ethyl- (2-hydroxyethyl) amino] -2- nitrobenzol-hydrochlorid (HC Blue No. 9), 1- (3-Hydroxy- propylamino) -4- [di (2-hydroxyethyl) amino] -2-nitrobenzol (HC Violet No. 2), l-Methylamino-4- [methyl- (2, 3-dihydroxypropyl) amino] -2- nitrobenzol (HC Blue No. 6), 2- ( (4-Amino-2-nitrophenyl) amino) -5- dimethylamino-benzoesäure (HC Blue No. 13), 1- (2-Aminoethylamino) - 4- [di (2-hydroxyethyl) amino] -2-nitrobenzol, 4- (Di (2- hydroxyethyl) amino) -2-nitro-l-phenylamino-benzol .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] -1- [ (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-hydroxypropylamino) -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 (2-hydroxyethyl) amino] -2-nitrobenzene, 4- (di (2-hydroxyethyl) amino) -2-nitro -l-phenylamino-benzene.
Nitrofarbstoffe (rot) : l-Amino-4- [ (2 -hydroxyethyl) amino] -2-nitrobenzol (HC Red No. 7), 2- Amino-4, 6-dinitro-phenol, 1, 4-Diamino-2-nitrobenzol (CI76070) , 4- Amino-2-nitro-diphenylamin (HC Red No. 1), l-Amino-4- [di (2- hydroxyethyl) amino] -2-nitrobenzol-hydrochlorid (HC Red No. 13), 1- Amino-5-chlor-4- [ (2 -hydroxyethyl) amino] -2-nitrobenzol, 4-Amino-l- [ (2 -hydroxyethyl) amino] -2 -nitrobenzol (HC Red No . 3), 4-((2- HydroxyethyDmethylamino) -1- (methylamino) -2-nitrobenzol, 1-Amino- 4- ( (2, 3-dihydroxypropyl) amino) -5-methyl-2-nitrobenzol, l-Amino-4- (methylamino) -2-nitrobenzol, 4-Amino-2-nitro-l- ( (prop-2-en-l-yl) - amino) -benzol, 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-nitrobenzol (HC Orange No. 2), 4- (2, 3-Dihydroxypropoxy) -1- [ (2-hydroxyethyl) amino] -2- nitrobenzol (HC Orange No . 3), l-Amino-5-chlor-4- [ (2, 3- dihydroxypropyl) amino] -2-nitrobenzol (HC Red No. 10), 5-Chlor-l,4- [di (2, 3 -dihydroxypropyl) amino] -2-nitrobenzol (HC Red No . 11), 2- [ (2 -Hydroxyethyl) amino] -4 , 6-dinitro-phenol, 4-Ethylamino-3- nitrobenzoesäure, 2- [ (4-Amino-2-nitrophenyl) amino] -benzoesäure, 2- Chlor-6-ethylamino-4-nitrophenol, 2-Amino-6-chlor-4-nitrophenol, 4- [ (3-Hydroxypropyl) amino] -3-nitrophenol, 2, 5-Diamino-6-nitro- pyridin, 6-Amino-3- ( (2-hydroxyethyl) amino) -2-nitropyridin, 3- Amino-6- ( (2-hydroxyethyl) amino) -2-nitropyridin, 3-Amino-6- (ethylamino) -2-nitropyridin, 3- ( (2-Hydroxyethyl) amino) -6- (methylamino) -2-nitropyridin, 3-Amino-6- (methylamino) -2- nitropyridin, 6- (Ethylamino) -3- ( (2 -hydroxyethyl) amino) -2- nitropyridin, 1,2,3, 4-Tetrahydro-6-nitrochinoxalin, 7-Amino-3, 4- dihydro-6-nitro-2H-l,4-benzoxazin (HC Red No. 14).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), l-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-l- [(2-hydroxyethyl) amino] -2-nitrobenzene (HC Red No. 3) , 4 - ((2-HydroxyethylMethylamino) -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- [(2nd -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 ) amino] -2-nitrobenzene (HC Red No. 10), 5-chloro-l, 4- [di (2,3-dihydroxy propyl) 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- nitrophenol, 4- [(3-hydroxypropyl) amino] -3-nitrophenol, 2, 5-diamino-6-nitro-pyridine, 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, 1,2,3, 4-tetrahydro-6-nitroquinoxaline , 7-amino-3,4,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14).
Nitrofarbstoffe (gelb) : l,2-Diamino-4-nitrobenzol (CI76020) , l-Amino-2- [ (2-hydroxy- ethyl) amino] -5-nitrobenzol (HC Yellow No. 5), 1- (2-Hydroxyethoxy) - 2- [ (2-hydroxyethyl) amino] -5-nitrobenzol (HC Yellow No. 4), l-[(2- Hydroxyethyl) amino] -2-nitrobenzol (HC Yellow No . 2), 2- (Di (2- hydroxyethyl) amino) -5-nitrophenol, 2- [ (2-Hydroxyethyl) amino] -1- methoxy-5-nitrobenzol, 2-Amino-3-nitrophenol, l-Amino-2-methyl-6- nitrobenzol, 1- (2-Hydroxyethoxy) -3-methylamino-4-nitrobenzol, 2,3- (Dihydroxypropoxy) -3-methylamino-4-nitrobenzol, 2- [ (2- Hydroxyethyl) amino] -5-nitrophenol (HC Yellow No. 11), 3-[(2- Aminoethyl) amino] -l-methoxy-4-nitrobenzol-hydrochlorid (HC Yellow No.9), 1- [ (2-Ureidoethyl) amino] -4-nitrobenzol, 4- [(2,3- Dihydroxypropyl) amino] -3-nitro-l-trifluormethyl-benzol (HC Yellow No. 6), l-Chlor-2, 4-bis [ (2-hydroxyethyl) amino] -5-nitrobenzol (HC Yellow No. 10), l-Amino-4- ( (2-aminoethyl) amino) -5-methyl-2- nitrobenzol, 4- [ (2-Hydroxyethyl) amino] -3-nitro-l-methylbenzol, 1- Chlor-4- [ (2 -hydroxyethyl) amino] -3-nitrobenzol (HC Yellow No. 12), 4- [ (2-Hydroxyethyl) amino] -3-nitro-l-trifluormethyl-benzol (HC Yellow No. 13), 4- [ (2-Hydroxyethyl) amino] -3-nitro-benzonitril (HC Yellow No. 14), 4- [ (2-Hydroxyethyl) amino] -3-nitro-benzamid (HC Yellow No. 15) 3- ( (2 -Hydroxyethyl) amino) -4-methyl-l-nitrobenzol, 4-Chlor-3- ( (2-hydroxyethyl) amino) -1-nitrobenzol .Nitro dyes (yellow): 1,2-diamino-4-nitrobenzene (CI76020), 1,2-amino-2- [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1- (2-hydroxyethoxy) -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-nitrophenol, 2- [(2-hydroxyethyl) amino] -1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, l-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- [(2nd , 3-dihydroxypropyl) amino] -3-nitro-1-trifluoromethyl-benzene (HC Yellow No. 6), 1-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- Ch lor-4- [(2-hydroxyethyl) amino] -3-nitrobenzene (HC Yellow No. 12), 4- [(2-Hydroxyethyl) amino] -3-nitro-1-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-1-nitrobenzene, 4-chlorine -3- ((2-hydroxyethyl) amino) -1-nitrobenzene.
Chinonfarbstoffe :Quinone dyes:
1, 4-Di [ (2 , 3-dihydroxypropyl) amino] -9, 10-anthrachinon, 1, 4-Di [ (2- hydroxyethyl) amino] -9, 10-anthrachinon (CI61545, Disperse Blue 23), 1- [ (2-Hydroxyethyl) amino] -4-methylamino-9, 10-anthrachinon (CI61505, Disperse Blue No. 3), 2- [ (2 -Aminoethyl) amino] -9, 10- anthrachinon (HC Orange No. 5), l-Amino-4-hydroxy-9, 10- anthrachinon (CI60710, Disperse Red 15), l-Hydroxy-4- [ (4-methyl-2- sulfophenyl) amino] -9, 10-anthrachinon, 7-Beta-D-glucopyranosyl- 9, 10-dihydro-l-methyl-9, 10-dioxo-3, 5,6, 8-tetrahydroxy-2- anthracencarbonsäure (CI75470, Natural Red 4), l-[(3- Aminopropyl) amino] -4-methylamino-9, 10-anthrachinon (HC Blue No. 8), 1- [ (3-Aminopropyl) amino] -9, 10-anthrachinon (HC Red No. 8), 1, 4-Diamino-2-methoxy-9, 10-anthrachinon (CI62015, Disperse Red No . 11, Solvent Violet No. 26), l,4-Dihydroxy-5, 8-bis [ (2-hydroxy- ethyl) amino] -9, 10-anthrachinon (CI62500, Disperse Blue No. 7, Solvent Blue No. 69), l,4-Diamino-9, 10-anthrachinon (CI61100, Disperse Violet No. 1), l-Amino-4- (methylamino) -9, 10-anthrachinon (CI61105, Disperse Violet No. 4, Solvent Violet No . 12), 2- Hydroxy-3-methoxy-l, 4-naphthochinon, 2, 5-Dihydroxy-l, 4- naphthochinon, 2-Hydroxy-3-methyl-l, 4-naphthochinon, N- (6- ( (3- Chlor-4- (methylamino) phenyl) imino) -4-methyl-3-oxo-l, 4- cyclohexadien-l-yl)harnstoff (HC Red No. 9), 2-((4-(Di(2- hydroxyethyl) amino) phenyl) amino) -5- ( (2-hydroxyethyl) amino) -2,5- cyclohexadien-l,4-dion (HC Green No. 1), 5-Hydroxy-l, 4- naphthochinon (CI75500, Natural Brown No. 7), 2-Hydroxy-l,4- naphthochinon (CI75480, Natural Orange No. 6), 1, 2-Dihydro-2- (1, 3- dihydro-3-oxo-2H-indol-2-yliden) -3H-indol-3-on (CI73000) , 4- ( (5- ( (2-Hydroxyethyl) amino-l-methyl-lH-pyrazol-4-yl) imino) -4,5- dihydro-5- ( (2 -hydroxyethyl) imino) -1-methyl-lH-Pyrazol- sulfat (1:1) ,hydrat (1:1) .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] -4-methylamino-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), l - [(3- Aminopropyl) amino] -4-methylamino-9, 10-anthraquinone (HC Blue No. 8), 1- [(3-aminopropyl) amino] -9, 10-anthraquinone (HC Red No. 8), 1, 4- Diamino-2-methoxy-9, 10-anthraquinone (CI62015, Disperse Red No. 11, Solvent Violet No. 26), 1,4-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, Disperse Violet No. 1), l-Amino-4- (methylamino) -9, 10-anthraquinone (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), 2- Hydroxy-3-methoxy-l, 4-naphthoquinone, 2,5-dihydroxy-l, 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 Red No. 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 Brown No. 7), 2-hydroxy-l, 4-naphthoquinone (CI75480, Natural Orange No. 6), 1, 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-1H-pyrazole-sul fat (1: 1), hydrate (1: 1).
Basische Farbstoffe: 9- (Dimethylamino) -benzo [a]phenoxazin-7-ium-chlorid (CI51175; Basic Blue No. 6), Di [4- (diethylamino) phenyl] [4- (ethyl- amino) naphthyl] carbenium-chlorid (CI42595; Basic Blue No. 7), Di- (4- (dimethylamino) phenyl) - (4- (methyl-phenylamino)naphthalin-l-yl) - carbenium-chlorid (CI42563; Basic Blue No . 8), 3,7- Di (dimethylamino) phenothiazin-5-ium-chlorid (CI52015 Basic Blue No. 9), Di [4- (dimethylamino) phenyl] [4- (phenyl- amino) naphthyl] carbenium-chlorid (CI44045; Basic Blue No. 26), 2- [ (4- (Ethyl (2 -hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methyl- benzothiazolium-methylsulfat (CI11154; Basic Blue No. 41), 8- Amino-2-brom-5-hydroxy-4-imino-6- [ (3-Basic dyes: 9- (dimethylamino) benzo [a] phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), di [4- (diethylamino) phenyl] [4- (ethylamino) naphthyl] carbenium -chloride (CI42595; Basic Blue No. 7), di- (4- (dimethylamino) phenyl) - (4- (methyl-phenylamino) naphthalene-l-yl) - carbenium chloride (CI42563; Basic Blue No. 8) , 3,7-Di (dimethylamino) phenothiazine-5-ium chloride (CI52015 Basic Blue No. 9), di [4- (dimethylamino) phenyl] [4- (phenylamino) naphthyl] carbenium chloride (CI44045; Basic Blue No. 26), 2- [(4- (ethyl (2-hydroxyethyl) amino) phenyl) azo] -6-methoxy-3-methylbenzothiazolium methyl sulfate (CI11154; Basic Blue No. 41), 8- Amino-2-bromo-5-hydroxy-4-imino-6- [(3-
(trimethylammonio) phenyl) amino] -1 (4H) -naphthalinon-chlorid (CI56059; Basic Blue No. 99), Bis [4- (dimethylamino) phenyl] [4- (methylamino) phenyl] carbenium-chlorid (CI42535; Basic Violet No. 1), Tri (4-amino-3-methylphenyl) carbenium-chlorid (CI42520; Basic Violet No. 2), Tris [4- (dimethylamino) phenyl] carbenium-chlorid(trimethylammonio) phenyl) amino] -1 (4H) -naphthalenone 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-(CI42555; Basic Violet No. 3), 2- [3,6-
(Diethylamino) dibenzopyranium-9-yl] -benzoesäurechlorid (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-methylbenzol (CI21010; Basic Brown No . 4), 1- [ (4-Aminophenyl) azo] -7- (trimethylammonio) -2- naphthol-Chlorid (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-(Diethylamino) dibenzopyranium-9-yl] benzoic acid chloride (CI45170, - Basic Violet No. 10), di (4-aminophenyl) (4-amino-3-methylphenyl) carbenium chloride (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-trimethylbenzolaminium chloride (CI112605, Basic Orange No. 69), 1- [( 4-amino-2-nitrophenyl) azo] -7-
(trimethylammonio) -2-naphthol-chlorid, 1- [ (4-Amino-3- nitrophenyl) azo] -7- (trimethylammonio) -2-naphthol-chlorid (CI12251; Basic Brown No. 17), 3 , 7-Diamino-2, 8-dimethyl-5-phenylphenazinium- chlorid (CI50240; Basic Red No. 2), 1, 4-Dimethyl-5- [ (4- (dimethyl- amino)phenyl) azo] -1, 2, 4-triazolium-chlorid (CI11055; Basic Red No . 22) , 2-Hydroxy-l- [ (2-methoxyphenyl) azo] -7- (trimethylammonio) - naphthalin-chlorid (CI12245; Basic Red No. 76), 2-[2-((2,4- Dimethoxyphenyl) amino) ethenyl] -1,3, 3-trimethyl-3H-indol-l-ium- chlorid (CI48055; Basic Yellow No. 11), 3-Methyl-l-phenyl-4- [ (3- (trimethylammonio) phenyl) azo] -pyrazol-5-on-chlorid (CI12719; Basic Yellow No. 57), Di [4- (dimethylamino) phenyl] iminomethan- hydrochlorid (CI41000; Basic Yellow No. 2), Bis[4-(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), 1, 4-Dimethyl-5- [(4- (dimethylamino) 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-indole-1-ium chloride (CI48055; Basic Yellow No. 11), 3-methyl-1-phenyl -4- [(3- (trimethylammonio) phenyl) azo] pyrazol-5-one chloride (CI12719; Basic Yellow No. 57), Di [4- (dimethylamino) phenyl] iminomethane hydrochloride (CI41000; Basic Yellow No. . 2 to 4-
(diethyla ino) phenyl] phenylcarbenium-hydrogensulfat (1:1)(diethyla ino) phenyl] phenylcarbenium hydrogen sulfate (1: 1)
(CI42040; Basic Green No . 1), Di (4- (dimethylamino) phenyl) - phenylmethanol (CI42000; Basic Green No. 4), 1- (2-(CI42040; Basic Green No. 1), Di (4- (dimethylamino) phenyl) phenylmethanol (CI42000; Basic Green No. 4), 1- (2-
Morpholiniumpropylamino) -4-hydroxy-9, 10-anthrachinon-methylsulfat, 1- [ (3- (Dimethyl-propylaminium)propyl) amino] -4- (methylamino) -9,10- anthrachinon-chlorid.Morpholinium propylamino) -4-hydroxy-9, 10-anthraquinone methyl sulfate, 1- [(3- (dimethylpropylaminium) propyl) amino] -4- (methylamino) -9,10-anthraquinone chloride.
Neutrale Azofarbstoffe:Neutral azo dyes:
1- [Di (2 -hydroxyethyl) amino] -3-methyl-4- [ (4-nitrophenyl) azo] -benzol (CI11210, Disperse Red No. 17), 1- [Di (2 -hydroxyethyl) amino] -4- [ (4- nitrophenyl) azo] -benzol (Disperse Black No. 9), 4-[(4- Aminophenyl) azo] -1- [di (2 -hydroxyethyl) amino] -3-methylbenzol (HC Yellow No. 7), 2, 6-Diamino-3- [ (pyridin-3-yl) azo] -pyridin, 2-((4- (Acetylamino) phenyl) azo) -4-methylphenol (CI11855; Disperse Yellow No. 3) .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-methylphenol (CI11855; Disperse Yellow No. 3).
Saure Farbstoffe : 6-Hydroxy-5- [ (4-sulfophenyl) azo] -2-naphthalinsulfonsäure- dinatriumsalz (CI15985; Food Yellow No . 3; FD&C Yellow No. 6), 2, 4-Dinitro-l-naphthol-7-sulfonsäure-dinatriumsalz (CI10316; Acid Yellow No. 1; Food Yellow No. 1), 2- (Indan-1, 3-dion-2-yl) chinolin- x,x-sulfonsäure (Gemisch aus Mono- und Disulfonsäure) (CI47005;D&C Yellow No . 10; Food Yellow No . 13; Acid Yellow No . 3) , 5-Hydroxy-l- (4-sulfophenyl) -4- [ (4-sulfophenyl) azo] pyrazol-3- carbonsäure-trinatriumsalz (CI19140; Food Yellow No. 4; Acid Yellow No. 23), 9- (2-Carboxyphenyl) -6-hydroxy-3H-xanthen-3-onAcid 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- (indan-1, 3-dion-2-yl) quinoline- 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-sulfophenyl) -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) benzolsulfonsäure-dinatriumsalz (CI13015, Acid Yellow No. 9), 5- [ (2, 4-Dinitrophenyl) amino] -2-phenylamino- benzolsulfonsäure-natriumsalz (CI10385; Acid Orange No. 3), 4-(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] -benzolsulfonsäure Mononatriumsalz[(2,4-Dihydroxyphenyl) azo] benzenesulfonic acid monosodium salt
(CI14270; Acid Orange No. 6), 4- [ (2-Hydroxynaphth-l-yl) azo] - benzolsulfonsäure-natriumsalz (CI15510; Acid Orange No. 7), 4-(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] - benzolsulfonsäure-natriumsalz (CI20170; Acid Orange No. 24), 4- Hydroxy-3- [ (4-sulfonaphth-l-yl) azo] -1-naphthalin-sulfonsäure- dinatriumsalz (CI14720; Acid Red No. 14), 4-Hydroxy-3- [ (2-methoxy- phenyl) azo] -1-naphthalinsulfonsäure-mononatriumsalz (CI14710; Acid Red No. 4), 6-Hydroxy-5- [ (4-sulfonaphth-l-yl) azo] -2 , 4-naphthalin- disulfonsäure-trinatriumsalz (CI16255; Ponceau 4R; Acid Red No. 18) , 3-Hydroxy-4- [ (4-sulfonaphth-1-yl) azo] -2 , 7-naphthalin- disulfonsäure-trinatriumsalz (CI16185; Acid Red No. 27), 8-Amino- l-hydroxy-2- (phenylazo) -3, 6-naphthalin-disulfonsäure-dinatriumsalz[(2,4-Dihydroxy-3- [(2,4-dimethylphenyl) azo] phenyl) azo] benzenesulfonic acid sodium salt (CI20170; Acid Orange No. 24), 4-hydroxy-3- [(4-sulfonaphth- l-yl) azo] -1-naphthalenesulfonic acid disodium salt (CI14720; Acid Red No. 14), 4-hydroxy-3- [(2-methoxyphenyl) azo] -1-naphthalenesulfonic acid monosodium salt (CI14710; acid Red No. 4), 6-Hydroxy-5- [(4-sulfonaphth-l-yl) azo] -2, 4-naphthalenedisulfonic acid trisodium salt (CI16255; Ponceau 4R; Acid Red No. 18), 3-Hydroxy -4- [(4-sulfonaphth-1-yl) azo] -2, 7-naphthalenedisulfonic acid trisodium salt (CI16185; Acid Red No. 27), 8-amino-1-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-naphthalin-disulfonsäure-dinatriumsalz(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) -benzoesäure-dinatriumsalz (CI45430; Acid Red No. 51), N- [6- (Diethylamino) -9- (2, 4-disulfophenyl) -3H-xanthen- 3 -yliden] -N-ethylethanammonium-hydroxid, inneres Salz, Natriumsalz (CI45100; Acid Red No. 52), 8- [ (4- (Phenylazo) phenyl) azo] -7- naphthol-1, 3 -disulfonsäure-dinatriumsalz (CI27290; Acid Red No. 73), 2 ' , 4 ' , 5 ' , 7 ' -Tetrabrom-3 ' , 6 ' -dihydroxyspiro [isobenzofuran- 1 (3H) , 9' - [9H] xanthen] -3-on-dinatriumsalz (CI45380 Acid Red No . 87) , 2' ,4' ,5' ,7' -Tetrabrom-4,5,6,7-tetrachlor-3' ,6' - dihydroxyspiro [isobenzofuran-1 (3H) ,9' [9H] xanthen] -3-on- dinatriu salz (CI45410; Acid Red No. 92), 3 ' , 6 ' -Dihydroxy-4 ' , 5 ' - diiodospiro [isobenzofuran-1 (3H) ,9' (9H) -xanthen] -3-on-dinatriumsalz (CI45425; Acid Red No . 95), 2-Hydroxy-3- ( (2-hydroxynaphth-l- yl)azo) -5-nitrobenzolsulfonsäure-mononatriumsalz (CI15685; Acid Red No. 184), (2-Sulfophenyl) di [4- (ethyl ( (4- sulfophenyl) methyl) amino) phenyl] -carbenium-dinatriumsalz Betain (CI42090; Acid Blue No . 9; FD&C Blue No . 1), 1 , 4-Bis [ (2-sulfθ-4- methylphenyl) amino] -9, 10-anthrachinon-dinatriumsalz (CI 61570; Acid Green No. 25), Bis [4- (dimethylamino) phenyl] - (3, 7-disulfo-2- hydroxynaphth-1-yl) carbenium-inneres Salz Mononatriumsalz (CI44090; Food Green No. 4; Acid Green No. 50), Bis[4- (diethylamino) phenyl] (2, 4 -disulfophenyl) carbenium-inneres salz, Natriumsalz (2:1) (CI42045; Food Blue No . 3; Acid Blue No. 1), Bis [4- (diethylamino) henyl] (5-hydroxy-2, 4 -disulfophenyl) carbenium- inneres salz, Calciumsalz (2:1) (CI42051; Acid Blue No . 3), 1- Amino-4- (cyclohexylamino) -9, 10-anthrachinon-2-sulfonsäure- natriumsalz (CI62045; Acid Blue No. 62), l-Amino-4- (phenylamino) - 9, 10-anthrachinon-2-sulfonsäure (CI62055; Acid Blue No. 25), 2- (1, 3-Dihydro-3-oxo-5-sulfo-2H-indol-2-yliden) -2, 3-dihydro-3-oxo- lH-indol-5-sulfonsäure-dinatriumsalz (CI73015; Acid Blue No. 74), 9- (2-Carboxyphenyl) -3- [ (2-methylphenyl) amino] -6- [ (2-methyl-4- sulfophenyl) amino] xanthylium-inneres Salz, mononatriumsalz (CI45190; Acid Violet No. 9), l-Hydroxy-4- [ (4-methyl-2- sulfophenyl) amino] -9, 10-anthrachinon-natriumsalz (CI60730; D&C Violett No. 2; Acid Violet No. 43), Bis [3-nitro-4- [ (4- phenylamino) -3-sulfo-phenylamino] -phenyl] -sulfon (CI10410; Acid Brown No. 13), 5-Amino-4-hydroxy-6- [ (4-nitrophenyl) azo] -3- (phenylazo) -2 , 7-naphthalin-disulfonsäure Dinatriumsalz (CI20470; Acid Black No. 1), 3-Hydroxy-4- [ (2-hydroxynaphth-l-yl) azo] -7- nitro-1-naphthalin-sulfonsäure-chromkomplex (3:2) (CI15711; Acid Black No. 52), 3- [ (2, 4 -Dimethyl-5-sulfophenyl) azo] -4-hydroxy-l- naphthalin-sulfonsäure-dinatriumsalz (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- naphthalindisulfonsäure-tetranatriumsalz (CI28440; Food Black No. 1) , 3-Hydroxy-4- (3-methyl-5-oxo-l-phenyl-4, 5-dihydro-lH-pyrazol-4- ylazo) -naphthalin-1-sulfonsäure-natriumsalz, Chrom-Komplex (Acid Red No. 195) .(CI18065; Acid Red No. 35), 2- (3-hydroxy-2, 4, 5, 7-tetraiododibenzopyran-6-one-9-yl) -benzoic acid disodium salt (CI45430; acid Red No. 51), N- [6- (diethylamino) -9- (2,4-disulfophenyl) -3H-xanthene-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 Red No. 73), 2 ', 4', 5 ', 7' tetrabromo- 3 ', 6' -dihydroxyspiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one-disodium salt (CI45380 Acid Red No. 87), 2', 4 ', 5', 7 '- Tetrabromo-4,5,6,7-tetrachloro-3 ', 6' - dihydroxyspiro [isobenzofuran-1 (3H), 9 '[9H] xanthene] -3-one-dinatriu salt (CI45410; Acid Red No. 92) , 3 ', 6' -Dihydroxy-4 ', 5' - diiodospiro [isobenzofuran-1 (3H), 9 '(9H) -xanthene] -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-see lfθ-4-methylphenyl) amino] -9, 10-anthraquinone disodium salt (CI 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) henyl ] (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) amino] 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-sulfophenylamino] phenyl] sulfone (CI10410; acid Brown No. 13), 5-Amino-4-hydroxy-6- [(4-nitrophenyl) azo] -3- (phenylazo) -2, 7-naphthalenedisulfonic acid disodium salt (CI20470; Acid Black No. 1), 3-hydroxy- 4- [(2-hydroxynaphth-l-yl) azo] -7-nitro-1-naphthalenesulfonic acid chromium complex (3: 2) (CI15711; Acid Black No. 52), 3- [(2, 4-dimethyl -5-sulfophenyl) azo] -4-hydroxy-1-naphthalenesulfonic 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- (3rd -methyl-5-oxo-l-phenyl-4,5-dihydro-lH-pyrazol-4-ylazo) -naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red No. 195).
Weitere zur Haarfärbung bekannte und übliche Farbstoffe, die in dem erfindungsgemäßen Färbemittel enthalten sein können, sind unter anderem in E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (1957), Seiten 503 ff. sowie H. Janistyn, "Handbuch der Kosmetika und Riechstoffe", Band 3 (1973), Seiten 388 ff. und K. Schrader "Grundlagen und Rezepturen der Kosmetika", 2. Auflage (1989), Seiten 782-815 beschrieben.Further dyes known and customary for dyeing hair, which may be present in the colorant according to the invention, can be found, inter alia, in E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (1957), pages 503 ff. And H Janistyn, "Handbook of Cosmetics and Fragrances", Volume 3 (1973), pages 388 ff. And K. Schrader "Fundamentals and Recipes of Cosmetics", 2nd edition (1989), pages 782-815.
Geeignete haarfärbende Pigmente sind im Anwendungsmedium praktisch unlösliche Farbmittel und können anorganisch oder organisch sein. Auch anorganisch-organische Mischpigmente sind möglich. Bei denSuitable 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. Both
Pigmenten handelt es sich vorzugsweise nicht um Nanopigmente . Die bevorzugte Teilchengröße beträgt 1 bis 200 μm, insbesondere 3 bis 150 μm, besonders bevorzugt 10 bis 100 μm. Bevorzugt sind anorganische Pigmente. Die anorganischen Pigmente können natürlichen Ursprungs sein, beispielsweise hergestellt aus Kreide, Ocker, U bra, Grünerde, gebranntem Terra di Siena oder Graphit. Bei den Pigmenten kann es sich um Weißpigmente wie z.B. Titandioxid oder Zinkoxid, um Schwarzpigmente wie z.B. Eisenoxidschwarz, Buntpigmente wie z.B. Ultramarin oder Eisenoxidrot, um Glanzpigmente, Metalleffekt-Pigmente, Perlglanzpigmente sowie um Fluoreszenz- oderPigments 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 inorganic pigments can be of natural origin, for example made from chalk, ocher, U bra, green earth, burnt terra di Siena or graphite. The pigments can 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 red, around luster pigments, metallic effect pigments, pearlescent pigments as well as around fluorescent or
Phosphoreszenzpigmente handeln, wobei vorzugsweise mindestens ein Pigment ein farbiges, nicht-weißes Pigment ist. Geeignet sind Metalloxide, -hydroxide und -oxidhydrate, Mischphasenpigmente, schwefelhaltige Silicate, Metallsulfide, komplexe Metallcyanide, Metallsulfate, -chromate und -molybdate sowie die Metalle selbst (Bronzepigmente) . Geeignet sind insbesondere Titandioxid (CI 77891) , schwarzes Eisenoxid (CI 77499) , gelbes Eisenoxid (CI 77492) , rotes und braunes Eisenoxid (CI 77491) , Manganviolett (CI 77742) , Ultramarine (Natrium-Aluminiumsulfosilikate, CI 77007, Pigment Blue 29) , Chromoxidhydrat (CI77289) , Eisenblau (Ferric Ferrocyanide, CI77510) , Carmine (Cochineal) . Besonders bevorzugt sind Pigmente auf Mica- bzw. Glimmerbasis welche mit einem Metalloxid oder einem Metalloxychlorid wie Titandioxid oder Wismutoxychlorid sowie gegebenenfalls weiteren farbgebenden Stoffen wie Eisenoxiden, Eisenblau, Ultramarine, Carmine etc. beschichtet sind und wobei die Farbe durch Variation der Schichtdicke bestimmt ist. Derartige Pigmente werden beispielsweise unter den Handelsbezeichnung Rona , Colorona , Dichrona und Timiron von der Firma Merck, Deutschland vertrieben. Organische Pigmente sind z.B. die natürlichen Pigmente Sepia, Gummigutt, Knochenkohle, Kasseler Braun, Indigo, Chlorophyll und andere Pflanzenpigmente. Synthetische organische Pigmente sind z.B. Azo-Pigmente, Anthrachinoide, Indigoide,Act phosphorescent pigments, preferably at least one pigment being a colored, non-white pigment. Metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates as well as the metals themselves (bronze pigments) are suitable. Titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29 ), Chromium Oxide Hydrate (CI77289), Iron Blue (Ferric Ferrocyanide, CI77510), Carmine (Cochineal). Pigments based on mica or mica are particularly preferred, which are coated with a metal oxide or a metal oxychloride such as titanium dioxide or bismuth oxychloride and optionally other colorants such as iron oxides, iron blue, ultramarine, carmine, etc., and the color is determined by varying the layer thickness. Pigments of this type are sold, for example, under the trade names Rona, Colorona, Dichrona and Timiron by Merck, Germany. Organic pigments are e.g. the natural pigments sepia, gum, bone char, Kasseler brown, indigo, chlorophyll and other plant pigments. Synthetic organic pigments are e.g. Azo pigments, anthraquinones, indigoids,
Dioxazin-, Chinacridon- , Phtalocyanin- , Isoindolinon-, Perylen- und Perinon- , Metallkomplex-, Alkaliblau- und Diketopyrrolopyrrolpigmente .Dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments.
Das erfindungsgemäße Haarbehandlungsmittel enthält vorzugsweise zusätzlich mindestens einen haarpflegenden Stoff in einer Menge von 0,01 bis 10, besonders bevorzugt von 0,05 bis 5 Gew.%. Bevorzugte haarpflegende Stoffe sind Silikonverbindungen sowie kationaktive Stoffe, die auf Grund von kationischen oder kationisierbaren Gruppen, insbesondere primären, sekundären, tertiären oder quaternären Amingruppen eine Substantivität zu menschlichem Haar aufweisen. Geeignete kationaktive Stoffe sind ausgewählt aus kationischen Tensiden, betainischen, amphoteren Tensiden, kationischen Polymeren, Silikonverbindungen mit kationischen oder kationisierbaren Gruppen, kationisch derivatisierten Proteinen oder Proteinhydrolysaten und Betain.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 silicone compounds and cationic substances which are based on cationic or cationizable groups, especially primary, secondary, tertiary or quaternary amine groups have a substantivity to human hair. Suitable cationic substances are selected from cationic surfactants, betaine, amphoteric surfactants, cationic polymers, silicone compounds with cationic or cationizable groups, cationically derivatized proteins or protein hydrolyzates and betaine.
Geeignete Silikonverbindungen sind z.B. Polydimethylsiloxan (INCI: Dimethicon) , α-Hydro-ω-hydroxypolyoxydimethylsilylen (INCI: Dimethiconol) , cyclisches Dimethylpolysiloxan (INCI: Cyclomethicon) , Trimethyl (octadecyloxy) silan (INCI: Stearoxy- trimethylsilan) , Dimethylsiloxan/Glykol Copolymer (INCI: Dimethicon Copolyol) , Dimethylsiloxan/Aminoalkylsiloxan Copolymer mit Hydroxyendgruppen (INCI: Amodimethicon), Monomethylpolysiloxan mit Laurylseitenketten und Polyoxyethylen- und/oder Polyoxypropylenendketten, (INCI: Laurylmethicon Copolyol), Dimethylsiloxan/Glykol Copolymeracetat (INCI: Dimethiconcopolyol Acetat) , Dimethylsiloxan/Aminoalkylsiloxan Copolymer mit Trimethylsilylendgruppen (INCI: Trimethylsilylamodimethicon) .Suitable silicone compounds are e.g. Polydimethylsiloxane (INCI: Dimethicone), α-Hydro-ω-hydroxypolyoxydimethylsilylene (INCI: Dimethiconol), cyclic Dimethylpolysiloxan (INCI: Cyclomethicone), Trimethyl (octadecyloxy) silane (INCI: Stearoxy-trimethylsilane), DimethylsiloxyI / Dimethylethiliconol / INC ), dimethylsiloxane / aminoalkylsiloxane copolymer having hydroxyl end groups (INCI: amodimethicone), monomethylpolysiloxane with Laurylseitenketten and polyoxyethylene and / or Polyoxypropylenendketten, (INCI: laurylmethicone copolyol), dimethylsiloxane / glycol Copolymeracetat (INCI: dimethicone copolyol acetate), dimethylsiloxane / aminoalkylsiloxane copolymer with trimethylsilyl end groups ( INCI: trimethylsilylamodimethicone).
Bevorzugte Silikonpolymere sind Dimethicone, Cyclomethicone und Dimethiconole . Auch Mischungen von Silikonpolymeren sind geeignet wie z.B. eine Mischung aus Dimethicon und Dimethiconol. Die vorstehend in Klammern angegebenen Bezeichnungen entsprechen der INCI Nomenklatur (International Cosmetic Ingredients) , wie sie zur Kennzeichnung kosmetischer Wirk- und Hilfsstoffe bestimmt sind.Preferred silicone polymers are dimethicones, cyclomethicones and dimethiconols. Mixtures of silicone polymers are also suitable, e.g. 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.
Üblicherweise können dem erfindungsgemäßen Haarbehandlungsmittel weitere bekannte kosmetische Zusatzstoffe beigefügt werden, z.B. nichtfestigende, nichtionische Polymere wie Polyethylenglykole, nichtfestigende, anionische und natürliche Polymere sowie deren Mischungen in einer Menge von vorzugsweise 0,01 bis 50 Gew.%. Auch Parfümöle in einer Menge von 0,01 bis 5 Gew.%, Trübungsmittel wie Ethylenglykoldistearat in einer Menge von 0,01 bis 5 Gew.%, Netzmittel oder Emulgatoren aus den Klassen der anionischen, kationischen, amphoteren oder nichtionischen Tenside wie Fettalkoholsulfate, ethoxylierte Fettalkohole, Fettsäurealkanolamide wie die Ester der hydrierten Rizinusölfettsäuren in einer Menge von 0,1 bis 30 Gew.%, außerdem Feuchthaltemittel, Anfärbestoffe, Lichtschutzmittel, Antioxidantien und Konservierungsstoffe in einer Menge von 0,01 bis 10 Gew.%.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 from the classes of anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid alkanolamides such as the esters of hydrogenated castor oil fatty acids in an amount of 0.1 to 30% by weight, as well as humectants, coloring agents, light stabilizers, antioxidants and Preservatives in an amount of 0.01 to 10% by weight.
Figur 1 zeigt schematisch das Verfahren zur Herstellung einer abrufbaren permanenten Frisurenform. Eine Haarsträhne wird auf einen Wickelkörper gewickelt und mit einer erfindungsgemäßen, ein vernetzbares Macromer enthaltenden Lösung besprüht. Durch Bestrahlung mit einer geeigneten Energiequelle, z.B. einer UV- Lampe wird die gewünschte permanente Form fixiert. Zum Schluß wird der Wickelkörper entfernt .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.
Figur 2 zeigt die Deformation einer permanenten Frisurenform und Wiederherstellung der permanenten Form aus der temporären Form. Die Haarlocke in der permanenten Form hat die Länge lo • Die Locke in der deformierten Form hat die Länge l . Die Locke in der wiederhergestellten Form hat die Länge 12 • DerFigure 2 shows the deformation of a permanent hairstyle shape and restoration of the permanent shape from the temporary shape. The curl in the permanent shape has the length lo • The curl in the deformed shape has the length l. The curl in the restored form has the length 1 2 • The
Wiederherstellungsgrad (Recovery) berechnet sich nach: Recovery = dl $ 12) / dl $ lθ) •Degree of recovery (recovery) is calculated according to: Recovery = dl $ 12) / dl $ lθ) •
Als Maß zur Beurteilung der Formgedächtniseigenschaften einer Zusammensetzung kann der Memory-Faktor dienen, in welchem sowohl die Umformbarkeit einer permanenten Frisurenform in eine temporäre Form (Formfaktor) als auch die Rückstellung der permanenten Form aus der temporären Form (Rückstellfaktor, Wiederherstellungsgrad) berücksichtigt werden. Wird von einer glatten Strähne ausgegangen, auf die eine Lockenform als permanente Form aufgeprägt wird und auf die anschließend eine zweite, glatte Form als temporäre Form aufgeprägt wird, so kann der Formfaktor bestimmt werden nach folgenden Kriterien: The memory factor can be used as a measure for assessing the shape memory properties of a composition, taking into account both the formability of a permanent hairstyle shape into a temporary shape (form factor) and the resetting of the permanent shape from the temporary shape (reset factor, degree of restoration). 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:
Der Rückstellfaktor kann bestimmt werden nach folgenden Kriterien:The reset factor can be determined according to the following criteria:
Der Memory-Faktor M ergibt sich aus dem jeweiligen Formfaktor f , dem maximalen Formfaktor F=4, dem jeweiligen Rückstellfaktor r und dem maximalen Rückstellfaktor R=6 gemäßThe 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 Der Memoryfaktor soll idealerweise nicht unter 25 liegen, bevorzugt zwischen 25 und 33,3, besonders bevorzugt zwischen 37 und 100.M = (f / F) * (r / R) * 100 The memory factor should ideally not be less than 25, preferably between 25 and 33.3, particularly preferably between 37 and 100.
Die nachfolgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern.The following examples are intended to explain the subject matter of the invention in more detail.
BeispieleExamples
Beispiel 1: Haarbehandlung mit einem Thermoset FormgedächtnispolymerExample 1: Hair treatment with a thermoset shape memory polymer
THF Ad 100 g λ > hergestellt gemäß Beispiel 2 der WO 99/42147 THF Ad 100 g λ> prepared according to Example 2 of WO 99/42147
Auf glatte Haarsträhnen einer Länge von je 19 cm wurden ca. l g der Zusammensetzung aufgebracht. Die Strähnen wurden auf Wickler gewickelt und getrocknet. Anschließend wurde auf ca. 65 bis 70 °C erwärmt und photochemisch (UV-Licht; Hg-Lampe oder Gesichtsbräuner) ausgehärtet . Nach Aushärtung und Abkühlung auf Raumtemperatur wurden die Wickler entfernt. Die Locken (aufgeprägte permanente Form) hatten eine Länge von 8 cm.Approx. 1 g of the composition was applied to straight strands of hair each 19 cm in length. The strands were wound on curlers and dried. The mixture was then heated to approximately 65 to 70 ° C. and cured photochemically (UV light; mercury lamp or facial tanner). After curing and cooling to room temperature, the winders were removed. The curls (stamped permanent shape) had a length of 8 cm.
Zur Simulation einer Deformation durch Kaltverformung wurden die Locken mit einem Gewicht von je 25 g beschwert und a) 1 Stunde, b) 2 Stunden und c) 3 Stunden bei Raumtemperatur ausgehängt. Die Längen der Locken nach Deformation betrugen a) 10 cm, b) 10 cm und c) 11,2 cm.To simulate a deformation due to cold working, the curls were weighed down with a weight of 25 g each and hung out a) 1 hour, b) 2 hours and c) 3 hours at room temperature. The lengths of the curls after deformation were a) 10 cm, b) 10 cm and c) 11.2 cm.
Nach Abnahme der Gewichte wurde auf ca. 65-70°C erwärmt. Die Locken zogen sich spontan zusammen auf Längen von a) 8 cm, b) 8 cm und c) 8,3 cm. Dies entspricht Wiederherstellungsgraden der aufgeprägten Frisurenform von a) 100 %, b) 100 % und c) 91 %. Der Wiederherstellungsgrad (Recovery) berechnet sich nach (vgl. Figur 2) : Recovery = (lχ - I2) / dl - lo)After the weights had been removed, the mixture was heated to approximately 65-70 ° C. The curls spontaneously contracted to lengths of a) 8 cm, b) 8 cm and c) 8.3 cm. This corresponds to degrees of recovery of the embossed hairstyle shape of a) 100%, b) 100% and c) 91%. The degree of recovery (recovery) is calculated according to (see FIG. 2): recovery = (lχ - I2) / dl - lo)
Zur Aufprägung einer zweiten Frisurenform (temporäre Form) wurde eine gewellte Strähne (Locke) einer Länge von 3,2 cm auf ca. 65- 70°C erwärmt, auf ihre ursprüngliche, volle Länge von 6,3 cm gestreckt und abgekühlt. Bei erneuter Erwärmung auf ca. 65-70°C zog sich die Locke spontan zusammen auf eine Länge von 3,9 cm. Dies entspricht einem Wiederherstellungsgrad der aufgeprägten Frisurenform von 77 %.To emboss a second hairstyle shape (temporary shape), a wavy strand (curl) with a length of 3.2 cm was heated to approx. 65-70 ° C, stretched to its original, full length of 6.3 cm and cooled. When heated again to approx. 65-70 ° C, the curl spontaneously contracted to a length of 3.9 cm. This corresponds to a degree of recovery of the embossed hairstyle shape of 77%.
Beispiele 2 bis 31: Haarbehandlung mit Formgedächtnispolymer Es wurden Zusammensetzungen hergestellt aus jeweils 2 Gew.% Macromer in einem Ethanol/Wasser-Gemisch (50/50) mit den folgenden Macromeren bzw. Macromermischungen mit den folgenden GewichtsverhältnissenExamples 2 to 31: Hair treatment with shape memory polymer Compositions were prepared from 2% by weight of macromer in an ethanol / water mixture (50/50) with the following macromers or macromer mixtures with the following weight ratios
Die Anwendung der Zusammensetzungen 2 bis 31 erfolgte wie bei Beispiel 1 beschrieben mit ähnlichen Ergebnissen.Compositions 2 to 31 were used as described in Example 1 with similar results.
Beispiele 32 bis 41: Haarbehandlung mit FormgedächtnispolymerExamples 32 to 41: Hair treatment with shape memory polymer
Es wurden Zusammensetzungen hergestellt aus jeweils 2 Gew.% Macromer in THF mit den folgenden Macromeren bzw. Macromermischungen mit den folgenden Gewichtsverhältnissen:Compositions were produced from 2% by weight of macromer in THF with the following macromers or macromer mixtures with the following weight ratios:
Die Anwendung der Zusammensetzungen 32 bis 41 erfolgte wie bei Beispiel 1 beschrieben mit ähnlichen Ergebnissen. Compositions 32 to 41 were used as described in Example 1 with similar results.
Beispiel 42: Haarbehandlung mit FormgedächtnispolymerExample 42: Hair treatment with shape memory polymer
Es wurde eine Zusammensetzung hergestellt aus 2 Gew.% PLGA(7k) -DMA Macromer in Ethylacetat und auf das Haar aufgebracht. Nachdem das Haar in Form gebracht wurde, wurde die Form durch Bestrahlung mit UV-Licht fixiert.A composition was prepared from 2% by weight PLGA (7k) -DMA macromer in ethyl acetate and applied to the hair. After the hair was shaped, the shape was fixed by irradiation with UV light.
Die Herstellung der in den Beispielen 2 bis 42 verwendeten Makromere erfolgte analog wie in der WO 99/42147 beschrieben.The macromers used in Examples 2 to 42 were prepared in a manner analogous to that described in WO 99/42147.
Die in den Beispielen verwendeten Abkürzungen bedeuten: PEG (4k) -DMA, PEG (8k) -DMA, PEG (10k) -DMA:The abbreviations used in the examples mean: PEG (4k) -DMA, PEG (8k) -DMA, PEG (10k) -DMA:
Poly (ethylenglykol) -dimethacrylat PPG- (475) -MA, PPG- (430) -MA: Poly (propylenglykol) -methacrylat PEG- (526) -MA: Poly (ethylenglykol) -methacrylat NθO-PPG(400) -MA, NoO-PPG (475) -MA: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 (propylenglykol) -methacrylat MeO-PEG- (300) -MA: Methyl-poly (ethylenglykol) -methacrylat MeO-PPG(200) -MA: Methyl-poly (propylenglykol) -methacrylat PLGA(7k) -DMA: Poly (L-lactid-co-glycolid) -dimethacrylat PCI (10k) -DMA: Poly (ε-caprolacton) -dimethacrylatNonyl-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
Beispiele 43-50: Haarbehandlung mit thermoplastischem FormgedächtnispolymerExamples 43-50: Hair treatment with thermoplastic shape memory polymer
Die Formgedächtnispolymere wurden hergestellt aus je zwei verschiedenen Makrodiolen und Trimethylhexan-1, 6-diisocaynat analog Beispiel 1 der WO 99/42147. Die Zusammensetzungen zur Haarbehandlung wurden hergestellt aus jeweils 0,5 Gew% Multiblock Copolymer in einem geeignetem Lösungsmittel oder Lösungsmittelgemisch wie z.B. Wasser, Ethanol, Tetrahydrofuran, Chloroform oder Gemischen dieser Lösungsmittel, insbesondereThe shape memory polymers were produced from two different macrodiols and trimethylhexane-1, 6-diisocaynate analogously to Example 1 of WO 99/42147. The hair treatment compositions were made from 0.5 wt% multiblock copolymer in a suitable solvent or solvent mixture such as e.g. Water, ethanol, tetrahydrofuran, chloroform or mixtures of these solvents, in particular
Tetrahydrofuran, Chloroform oder einem Wasser/Ethanol/THF Gemisch.Tetrahydrofuran, chloroform or a water / ethanol / THF mixture.
Die Abkürzungen der Makrodiole bedeuten:The abbreviations of the macrodiols mean:
PDX : Poly (para-dioxanon)PDX: poly (para-dioxanone)
PLGA: Poly (L-lactid-co-glycolid)PLGA: poly (L-lactide-co-glycolide)
PCL: Poly (ε-caprolacton)PCL: poly (ε-caprolactone)
PDL: Poly (pentadecalacton)PDL: poly (pentadecalactone)
Die Zahlenangaben bei den Bezeichnungen der Makrodiole stehen jeweils für das ungefähre Molekulargewicht der Makrodiole (± 100)The numerals in the names of the macrodiols each represent the approximate molecular weight of the macrodiols (± 100)
Auf eine glatte Haarsträhne wurden 7 g der Zusammensetzung aufgebracht. Die Strähne wurde auf einen Wickler gewickelt und getrocknet. Anschließend wurde auf ca. 95°C erwärmt. Nach Abkühlung auf Raumtemperatur (etwa 25 °C) wurde der Wickler entfernt. Die Locke (aufgeprägte permanente Form) hatte eine Länge von 4,5 cm .7 g of the composition were applied to a straight strand of hair. The tress was wound on a winder and dried. The mixture was then heated to about 95 ° C. After cooling to room temperature (about 25 ° C) the winder was removed. The curl (stamped permanent shape) had a length of 4.5 cm.
Zur Aufprägung einer zweiten Frisurenform (temporäre Form) wurde die gewellte Strähne auf ca. 55 °C erwärmt, auf ihre ursprüngliche, volle Länge gestreckt (16 cm) und auf Raumtemperatur abgekühlt. Bei erneuter Erwärmung auf ca. 55 °C zog sich die Locke spontan zusammen auf eine Länge von 8 cm. Dies entspricht einemTo emboss a second hairstyle shape (temporary shape), the wavy strand was warmed to approx. 55 ° C, stretched to its original, full length (16 cm) and cooled to room temperature. When heated again to approx. 55 ° C, the curl spontaneously contracted to a length of 8 cm. This corresponds to one
Wiederherstellungsgrad der aufgeprägten Frisurenform von ca. 70%. Recovery level of the embossed hairstyle shape of approx. 70%.

Claims

Patentansprüche claims
1. Verfahren zur Haarbehandlung, wobei1. A method of hair treatment, wherein
- eine WirkstoffZusammensetzung auf das Haar aufgebracht wird, wobei die WirkstoffZusammensetzung mindestens einen- An active ingredient composition is applied to the hair, the active ingredient composition at least one
Wirkstoff enthält, der ausgewählt ist aus Stoffen, welche alleine oder in Kombination mit weiteren Stoffen in der Lage sind, nach Aufbringung auf Haaren und nach Durchführung der im folgenden beschriebenen Behandlung den Haaren einen Formgedächtnis-Effekt zu verleihen; vorher, gleichzeitig oder nach dem Aufbringen der WirkstoffZusammensetzung das Haar in eine bestimmte Form (permanente Gedächtnisform) gebracht wird und anschließend die Gedächtnisform durch Induzierung einer chemischen oder physikalischen Veränderung der aufgebrachten Wirkstoffe fixiert wird; wobei nach einer gewollten oder ungewollten Deformation der Gedächtnisform die ursprüngliche Gedächtnisform durch eine physikalische Stimulation im wesentlichen wiederherstellbar ist.Contains active ingredient which is selected from substances which, alone or in combination with other substances, are able to impart a shape memory effect to the hair after application to hair and after the treatment described below; 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.
2. Verfahren nach Anspruch 1, wobei2. The method of claim 1, wherein
- die WirkstoffZusammensetzung mindestens ein vernetz-bares Makromer enthält, welches nach Vernetzung ein Formgedächtnispolymer bildet, wobei das Makromer a) vernetzbare Bereiche enthält, die durch chemische- The active substance composition contains at least one cross-linkable macromer, which forms a shape-memory polymer after cross-linking, the macromer a) containing cross-linkable areas that are chemically
Bindungen vernetzbar sind und b) thermoplastische Bereiche enthalten, die nicht chemisch vernetzbar sind, - die Gedächtnisform durch chemische Vernetzung des Makromers unter Ausbildung des Formgedächtnispolymers fixiert wird, und wobei das Formgedächtnispolymer mindestens eine Übergangstemperatur Ttrans aufweist. Bonds are crosslinkable and b) contain thermoplastic areas that are not chemically crosslinkable, the memory shape is fixed by chemical crosslinking of the macromer to form the shape memory polymer, and the shape memory polymer has at least one transition temperature Ttrans.
3. Verfahren zur Haarbehandlung, wobei eine durch ein Verfahren nach Anspruch 1 oder 2 programmierte Frisur (permanente Form) auf eine Temperatur oberhalb Ttrans erwärmt wird, das Haar in eine zweite (temporäre) Form gebracht wird und die zweite Form durch Abkühlen auf eine Temperatur unterhalb Ttrans fixiert wird.3. A method for hair treatment, wherein a hairstyle (permanent shape) programmed by a method according to claim 1 or 2 is heated to a temperature above Ttrans, the hair is brought into a second (temporary) shape and the second shape is cooled to a temperature is fixed below Ttrans.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das vernetzbare Makromer ausgewählt ist aus Verbindungen der allgemeinen Formel4. 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) wobei AI und A2 für reaktive, chemisch vernetzbare Gruppen stehen und -(X)n- für ein divalentes, thermoplastischesAl- (X) n -A2 (I) where AI and A2 are reactive, chemically crosslinkable groups and - (X) n- is a divalent, thermoplastic
Polymer- oder Oligomersegment steht .Polymer or oligomer segment stands.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass das vernetzbare Makromer ausgewählt ist aus mit mindestens zwei Acrylat- oder Methacrylatgruppen substituierten Polyestern, Oligoestern, Polyalkylenglykolen, Oligoalkylenglykolen, Polyalkylencarbonaten und Oligoalkylencarbonaten.5. The method according to claim 4, 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.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das vernetzbare Makromer ausgewählt ist aus Poly (ε-caprolacton) - dimethacrylat, Poly (DL-lactid) -dimethacrylat , Poly (L-lactid-co- glycolid) -dimethacrylat, Poly (ethylenglykol) dimethacrylat, Poly (propylenglykol) dimethacrylat, PEG-block-PPG-block-PEG- dimethacrylat, Poly (ethylenadipat) -dimethacrylat, Hexamethylencarbonatdimethacrylat .6. The method according to claim 5, 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.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in der Zusammensetzung zusätzlich ein Makromer mit nur einer end- oder seitenständigen, chemisch reaktiven Gruppe enthalten ist.7. The method according to any one of the preceding claims, characterized in that an additional in the composition Macromer with only one terminal or pendant, chemically reactive group is included.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das zusätzliche Makromer ausgewählt ist aus Verbindungen der allgemeinen Formel8. 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) wobei R für einen monovalenten organischen Rest, A3 für eine reaktive, chemisch vernetzbare Gruppe und -(X')n- für ein divalentes, thermoplastisches Polymer- oder Oligomersegment steht .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.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das zusätzliche Makromer ausgewählt ist aus mit einer Acrylat- oder Methacrylatgruppe substituierten Polyalkylenglykolen, deren Monoalkylether sowie deren Blockcopolymere .9. The method according to claim 8, characterized in that the additional macromer is selected from polyalkylene glycols substituted with an acrylate or methacrylate group, their monoalkyl ethers and their block copolymers.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das zusätzliche, mit nur einer chemisch reaktiven Gruppe substituierte Makromer ausgewählt ist aus Poly-10. The method according to claim 9, characterized in that the additional macromer substituted with only one chemically reactive group is selected from poly
(ethylenglykol) monoacrylat , Poly (propylenglykol) monoacrylat und deren Monoalkylether.(ethylene glycol) monoacrylate, poly (propylene glycol) monoacrylate and their monoalkyl ether.
11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der WirkstoffZusammensetzung mindestens zwei Wirkstoffe enthalten sind, die einzeln keine oder nur schwache11. 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
Formgedächtniseigenschaften aufweisen und die bei gemeinsamer Anwendung gemäß dem Verfahren nach Anspruch 1 Haaren einen synergistisch gesteigerten Formgedächtnis-Effekt verleihen.Have shape memory properties and, when used together in accordance with the method of claim 1, give hair a synergistically increased shape memory effect.
12. Verfahren nach Anspruch 1, wobei12. The method of claim 1, wherein
- die WirkstoffZusammensetzung mindestens ein Formge- dächtnispolymer enthält, welches a) mindestens ein durch physikalische Wechselwirkung vernetzbares hartes Segment mit einer ersten Übergangstemperatur T'trans» die oberhalb Raumtemperatur liegt, und b) mindestens ein weiches Segment mit einer zweiten- The active ingredient composition contains at least one 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
Übergangstemperatur Ttrans» welche unterhalb von T'trans liegt, aufweist und die Gedächtnisform durch physikalische Vernetzung der Formgedächtnispolymere fixiert wird.Transition temperature Ttrans », which is below T'trans, and the memory shape is fixed by physical crosslinking of the shape memory polymers.
13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die13. The method according to claim 12, characterized in that the
Formgebung der Haare unter Erwärmung auf eine Temperatur von mindestens T'trans erfolgt und dass die anschließende Fixierung der Haarform durch Abkühlung auf eine Temperatur unterhalb T'trans erfolgt.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.
14. Verfahren zur Haarbehandlung, wobei eine durch ein Verfahren nach Anspruch 12 oder 13 programmierte Frisur (permanente Form) auf eine Temperatur zwischen T'trans und Tt ans erwärmt wird, das Haar in eine zweite (temporäre) Form gebracht wird und die zweite Form durch Abkühlen auf eine Temperatur unterhalb Ttrans fixiert wird.14. A method for hair treatment, wherein a hairstyle (permanent shape) programmed by a method according to claim 12 or 13 is heated to a temperature between T'trans and d Tt ans, the hair is brought into a second (temporary) shape and the second Form is fixed by cooling to a temperature below Ttrans.
15. Verfahren zur Umprogrammierung einer zuvor durch ein Verfahren nach Anspruch 12 programmierten Frisur (permanente Form) in eine neue permanente Form, wobei15. A method for reprogramming a hairstyle (permanent shape) previously programmed by a method according to claim 12 into a new permanent shape, wherein
- die Frisur auf eine Temperatur oberhalb T'trans erwärmt wird- The hairstyle is heated to a temperature above T'trans
- in eine neue Form gebracht wird und - anschließend die neue Form durch Abkühlen auf eine Temperatur unterhalb T'trans fixiert wird.- is brought into a new shape and - the new shape is then fixed by cooling to a temperature below T'trans.
16. Verfahren nach einem der Ansprüche 12 bis 15, dadurch gekennzeichnet, dass das Formgedächtnispolymer einen Kristallinitätsgrad von 3 bis 80% aufweist und dass das Verhältnis der Elastizitätsmodule unterhalb und oberhalb von Ttrans mindestens 20 beträgt.16. The method according to any one of claims 12 to 15, characterized in that the shape memory polymer Has degree of crystallinity of 3 to 80% and that the ratio of the elastic modulus below and above Ttrans is at least 20.
17. Verfahren nach einem der Ansprüche 12 bis 16, dadurch gekennzeichnet, dass das Formgedächtnispolymer ein Copolyester-urethan ist .17. The method according to any one of claims 12 to 16, characterized in that the shape memory polymer is a copolyester urethane.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, dass das Formgedächtnispolymer das Reaktionsprodukten aus (a) zwei verschiedenen Macrodiolen, ausgewählt aus α,ω-Dihydroxy- polyestern, α,ω-Dihydroxy-oligoestern, α,ω-Dihydroxy- polylactonen und α,ω-Dihydroxy-oligolactonen und (b) mindestens einem Diisocyanat ist.18. The method according to claim 17, characterized in that the shape memory polymer, 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.
19. Verfahren zur Wiederherstellung einer zuvor durch ein19. Procedure to restore a previously through one
Verfahren nach Anspruch 1, 2, 11, 12 oder 15 programmierten Frisur (permanente Form) , wobei eine Frisur in einer temporären Form gemäß Anspruch 3 oder Anspruch 14 oder eine durch Kaltverformung deformierte Frisur auf eine Temperatur oberhalb Ttrans erwärmt wird.Method according to claim 1, 2, 11, 12 or 15 programmed hairstyle (permanent shape), wherein a hairstyle in a temporary shape according to claim 3 or claim 14 or a cold-deformed hairstyle is heated to a temperature above Ttrans.
20. Kosmetische Zusammensetzung enthaltend in einer geeigneten kosmetischen Grundlage mindestens einen Wirkstoff, der ausgewählt ist aus Stoffen, welche alleine oder in20. Cosmetic composition containing in a suitable cosmetic base at least one active ingredient which is selected from substances which are used alone or in
Kombination mit weiteren Stoffen in der Lage sind, nach Aufbringung auf Haaren und nach Durchführung eines Verfahrens nach einem der Ansprüche 1 bis 19 den Haaren einen Formgedächtnis-Effekt zu verleihen.Combination with other substances are able to impart a shape memory effect to the hair after application to hair and after carrying out a method according to one of claims 1 to 19.
21. Zusammensetzung nach Anspruch 20, dadurch gekennzeichnet, dass der Wirkstoff ein zu einem Formgedächtnispolymer vernetzbares Makromer ist, wobei das vernetzte Formgedächtnispolymer mindestens eine Übergangstemperatur Ttrans aufweist und wobei das Makromer a) vernetzbare Bereiche enthält, die durch chemische21. The composition according to claim 20, characterized in that the active ingredient is a macromer which can be crosslinked into a shape memory polymer, the crosslinked shape memory polymer has at least one transition temperature Ttrans and wherein the macromer a) contains crosslinkable regions which are chemically
Bindungen vernetzbar sind und b) thermoplastische Bereiche enthält, die nicht chemisch vernetzbar sind.Bonds are crosslinkable and b) contains thermoplastic areas that are not chemically crosslinkable.
22. Zusammensetzung nach Anspruch 20, dadurch gekennzeichnet, dass der Wirkstoff ein Formgedächtnispolymer ist, welches a) mindestens ein durch physikalische Wechselwirkung vernetzbares hartes Segment mit einer ersten Übergangstemperatur T'trans» die oberhalb Raumtemperatur liegt, und b) mindestens ein weiches Segment mit einer zweiten Übergangstemperatur Ttrans» welche unterhalb von T'trans liegt, aufweist.22. The composition according to claim 20, characterized in that the active ingredient is a shape memory polymer which a) at least one hard segment which 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 transition temperature Ttrans »which is below T'trans.
23. Zusammensetzung nach Anspruch 20, dadurch gekennzeichnet, dass mindestens zwei Wirkstoffe enthalten sind, die einzeln keine oder nur schwache Formgedächtniseigenschaften aufweisen und bei gemeinsamer Anwendung gemäß dem Verfahren nach Anspruch 1 Haaren einen synergistisch gesteigerten Formgedächtnis-Effekt verleihen.23. The composition according to claim 20, characterized in that it contains at least two active ingredients which individually have no or only weak shape memory properties and, when used together according to the method of claim 1, give hair a synergistically increased shape memory effect.
24. Zusammensetzung nach einem der Ansprüche 20 bis 23, dadurch gekennzeichnet, dass zusätzlich 0,01 bis 25 Gew.% mindestens eines Wirkstoffes enthalten sind, ausgewählt aus haarpflegenden Stoffen, haarfestigenden Stoffen und haarfärbenden Stoffen.24. The composition according to any one of claims 20 to 23, 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.
25. Kosmetisches Mittel enthaltend eine Zusammensetzung nach einem der Ansprüche 20 bis 24, dadurch gekennzeichnet, dass es in Form einer Lotion, einer Sprühlotion, einer Creme, eines Gels, eines Gelschaums, eines Aerosolsprays, eines Non- aerosolsprays, eines Aerosolschaums, eines Non-aerosolschaums, einer O/W- oder W/O-Emulsion, einer Mikroemulsion oder eines Haarwachses vorliegt.25. Cosmetic composition containing a composition according to any one of claims 20 to 24, 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 sprays, an aerosol foam, a non-aerosol foam, an O / W or W / O emulsion, a microemulsion or a hair wax.
26. Verwendung von zu Formgedächtnispolymeren vernetzbaren Makromeren zur Haarbehandlung, wobei die Makromere a) vernetzbare Bereiche enthalten, die durch chemische26. Use of macromers which can be crosslinked to form memory polymers for hair treatment, the macromers a) comprising crosslinkable regions which are chemically
Bindungen vernetzbar sind und b) thermoplastische Bereiche enthalten, die nicht chemisch vernetzbar sind und wobei die Formgedächtnispolymere mindestens eine Übergangstemperatur Ttrans aufweisen.Bonds are crosslinkable and b) contain thermoplastic areas that are not chemically crosslinkable and wherein the shape memory polymers have at least one transition temperature Ttrans.
27. Verwendung von physikalisch vernetzbaren Formgedächtnis- polymeren zur Haarbehandlung, wobei die Formgedächtnis- polymere a) mindestens ein durch physikalische Wechselwirkung vernetzbares hartes Segment mit einer ersten Übergangstemperatur T'trans» die oberhalb Raumtemperatur liegt, und b) mindestens ein weiches Segment mit einer zweiten27. Use of physically cross-linkable shape memory polymers for hair treatment, the shape memory polymers a) at least one hard segment that can be cross-linked 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
Übergangstemperatur Ttrans» welche unterhalb von T'trans liegt, aufweisen. Transition temperature Ttrans »which is below T'trans have.
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DE2002128120 DE10228120B4 (en) 2002-06-24 2002-06-24 Means and methods for hair treatment with shape memory polymers
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10215858A1 (en) * 2002-04-10 2004-03-18 Mnemoscience Gmbh Process for hair treatment with shape memory polymers
BR0304411A (en) * 2002-04-10 2004-07-27 Mnemoscience Gmbh Process for producing impression memory effects on hair by combining impression memory polymers with cationative active substances
DE10217351B3 (en) 2002-04-18 2004-02-12 Mnemoscience Gmbh Interpenetrating networks
US7976936B2 (en) 2002-10-11 2011-07-12 University Of Connecticut Endoprostheses
US7794494B2 (en) 2002-10-11 2010-09-14 Boston Scientific Scimed, Inc. Implantable medical devices
EP1558671B1 (en) 2002-10-11 2011-02-16 University of Connecticut Blends of amorphous and semicrystalline polymers having shape memory properties
US7524914B2 (en) 2002-10-11 2009-04-28 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
WO2004033553A1 (en) 2002-10-11 2004-04-22 University Of Connecticut Crosslinked polycyclooctene
EP2260882B1 (en) 2002-10-11 2020-03-04 Boston Scientific Limited Implantable medical devices
DE10300271A1 (en) 2003-01-08 2004-07-22 Mnemoscience Gmbh Photosensitive polymer networks
KR101108908B1 (en) * 2003-04-21 2012-01-31 카오카부시키가이샤 Mascara applicator
DE10334788A1 (en) * 2003-07-30 2005-02-24 Mnemoscience Gmbh Method of producing shape memory effects on hair in combination with hydrophobic agents
DE602004028079D1 (en) 2003-08-06 2010-08-26 Kao Corp Cosmetic aerosol composition
US8043361B2 (en) 2004-12-10 2011-10-25 Boston Scientific Scimed, Inc. Implantable medical devices, and methods of delivering the same
EP1871306A4 (en) 2005-04-01 2012-03-21 Univ Colorado A graft fixation device and method
DE102005017465A1 (en) 2005-04-14 2006-10-19 Beiersdorf Ag Polymer combination with nonionic polymers for cosmetic preparations
CN101395202B (en) 2006-03-03 2012-01-18 帝斯曼知识产权资产管理有限公司 Hair care compositions
DE102006012169B4 (en) * 2006-03-14 2007-12-13 Gkss-Forschungszentrum Geesthacht Gmbh Shape memory polymer with polyester and polyether segments, process for its preparation and shape programming and use
ATE536248T1 (en) * 2006-03-23 2011-12-15 Helmholtz Zentrum Geesthacht IONIC STRENGTH SENSITIVE SHAPE MEMORY POLYMERS AND SHAPE MEMORY COMPOSITIONS
DE102006017759A1 (en) * 2006-04-12 2007-10-18 Gkss-Forschungszentrum Geesthacht Gmbh Shape memory polymer with polyester and polyacrylic segments and methods for its preparation and programming
US7846361B2 (en) 2006-07-20 2010-12-07 Orbusneich Medical, Inc. Bioabsorbable polymeric composition for a medical device
US20080085946A1 (en) * 2006-08-14 2008-04-10 Mather Patrick T Photo-tailored shape memory article, method, and composition
CN103212115B (en) 2006-10-20 2016-09-14 奥巴斯尼茨医学公司 Bioabsorbable polymer composition and armarium
US7959942B2 (en) 2006-10-20 2011-06-14 Orbusneich Medical, Inc. Bioabsorbable medical device with coating
US8263057B2 (en) 2006-12-18 2012-09-11 Avon Products, Inc. Mascara composition containing shape-memory polymers, gels, and fibers
EP2296619B1 (en) * 2008-06-19 2015-10-07 DSM IP Assets B.V. Shampoo preparations
JP5978539B2 (en) * 2008-06-19 2016-08-24 ディーエスエム アイピー アセッツ ビー.ブイ. Shampoo formulation
US8069858B2 (en) * 2008-07-24 2011-12-06 Medshape Solutions, Inc. Method and apparatus for deploying a shape memory polymer
US20100170521A1 (en) * 2008-07-24 2010-07-08 Medshape Solutions, Inc. Method and apparatus for deploying a shape memory polymer
US8430933B2 (en) * 2008-07-24 2013-04-30 MedShape Inc. Method and apparatus for deploying a shape memory polymer
US9422964B2 (en) 2009-04-10 2016-08-23 3M Innovative Properties Company Blind fasteners
EP2417366B1 (en) 2009-04-10 2015-02-25 3M Innovative Properties Company Blind fasteners
WO2010144548A2 (en) 2009-06-09 2010-12-16 Regear Life Sciences, Inc. Shielded diathermy applicator with automatic tuning and low incidental radiation
JP5608226B2 (en) * 2009-06-16 2014-10-15 スリーエム イノベイティブ プロパティズ カンパニー Peelable adhesive article
EP2501976B1 (en) 2009-11-16 2017-10-04 3M Innovative Properties Company Pipe section joining
JP5774020B2 (en) 2009-11-24 2015-09-02 スリーエム イノベイティブ プロパティズ カンパニー Articles and methods using shape memory polymers
FR2961396B1 (en) * 2010-06-16 2013-03-15 Oreal PROCESS FOR MAKE-UP OR CARE OF KERATIN FIBERS USING RETRACTABLE FIBERS AND USE THEREOF
WO2012050691A2 (en) 2010-09-30 2012-04-19 3M Innovative Properties Company Writing device with deformable grip and method of making same
US8974217B2 (en) 2010-11-11 2015-03-10 Spirit Aerosystems, Inc. Reconfigurable shape memory polymer tooling supports
US8734703B2 (en) 2010-11-11 2014-05-27 Spirit Aerosystems, Inc. Methods and systems for fabricating composite parts using a SMP apparatus as a rigid lay-up tool and bladder
US8815145B2 (en) 2010-11-11 2014-08-26 Spirit Aerosystems, Inc. Methods and systems for fabricating composite stiffeners with a rigid/malleable SMP apparatus
US8877114B2 (en) 2010-11-11 2014-11-04 Spirit Aerosystems, Inc. Method for removing a SMP apparatus from a cured composite part
US9427493B2 (en) 2011-03-07 2016-08-30 The Regents Of The University Of Colorado Shape memory polymer intraocular lenses
BR112014001254A2 (en) 2011-07-19 2017-02-21 3M Innovative Properties Co thermosetting adhesive article and methods of preparation and use thereof
WO2013090311A1 (en) * 2011-12-13 2013-06-20 Avon Products, Inc. Methods and compositions to impart memory effects onto biosurfaces
KR102058512B1 (en) 2012-07-26 2019-12-23 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Heat de-bondable optical articles
KR20150038203A (en) 2012-07-26 2015-04-08 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Heat de-bondable adhesive articles
EP2712609A1 (en) 2012-09-26 2014-04-02 Bayer MaterialScience AG Polyurethane-urea compound for skin and hair cosmetics
US9982163B2 (en) 2012-10-05 2018-05-29 Syracuse University Waterborne shape memory polymer coatings
EP3083168A1 (en) * 2013-12-16 2016-10-26 3M Innovative Properties Company Systems and methods for dispensing polymer fasteners
US10250799B2 (en) 2014-05-21 2019-04-02 Google Technology Holdings LLC Enhanced image capture
FR3043549B1 (en) * 2015-11-12 2018-12-07 L'oreal PROCESS FOR TREATING KERATIN FIBERS WITH A COMPOSITION COMPRISING A RETICULATING AGENT AND A STEAM IRON
FR3045376B1 (en) 2015-12-22 2018-02-16 L'oreal A CAPILLARY TREATMENT PROCESS USING A COMPOSITION COMPRISING AT LEAST ONE CATIONIC ACRYLIC COPOLYMER
US20170189308A1 (en) * 2015-12-31 2017-07-06 L'oreal Compositions and methods for treating keratinous substrates
US20170189307A1 (en) * 2015-12-31 2017-07-06 L'oreal Compositions and methods for treating keratinous substrates
US10272026B2 (en) 2017-07-31 2019-04-30 L'oreal Water-in-oil emulsion compositions suitable for altering the color of hair

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579630A (en) * 1966-12-29 1971-05-18 Allied Chem Treating the hair with oxazoline polymer and copolymer hair dressing formulations
US5506300A (en) * 1985-01-04 1996-04-09 Thoratec Laboratories Corporation Compositions that soften at predetermined temperatures and the method of making same
AU5302086A (en) * 1985-01-04 1986-07-29 Thoratec Laboratories Corp. Compositions that soften at predetermined temperatures and the method of making same
JPH02118178A (en) * 1988-10-28 1990-05-02 Mitsubishi Heavy Ind Ltd Fibrous sheet with shape memory and provision of fibrous sheet product with shape memory nature
JPH02121907A (en) * 1988-10-31 1990-05-09 Mitsubishi Heavy Ind Ltd Cosmetic for human
JPH0441416A (en) * 1990-06-07 1992-02-12 Noevir Co Ltd Cosmetic for hair
JPH0747642B2 (en) * 1990-06-18 1995-05-24 旭化成工業株式会社 Shape memory resin emulsion and manufacturing method thereof
US5362486A (en) * 1992-04-10 1994-11-08 Helene Curtis, Inc. In-situ polymerization of oligomers onto hair
DE69521116T2 (en) * 1994-01-27 2001-10-25 Kao Corp HAIR COSMETIC COMPOSITION
US5442037A (en) * 1994-09-07 1995-08-15 Tong Yang Nylon Co., Ltd. Polyester prepolymer showing shape-memory effect
DK1062278T3 (en) * 1998-02-23 2006-09-25 Mnemoscience Gmbh Polymers with shape memory
RU2215542C2 (en) * 1998-02-23 2003-11-10 Массачусетс Инститьют Оф Текнолоджи Biodecomposing polymers able recovery of form
KR20010041801A (en) * 1998-03-11 2001-05-25 그래햄 이. 테일러 Structures and fabricated articles having shape memory made from alpha-olefin/vinyl or vinylidene aromatic and/or hindered aliphatic vinyl or vinylidene interpolymers
DE10000807A1 (en) * 2000-01-12 2001-07-19 Basf Ag Process for the treatment of a cosmetic agent by irradiation with NIR radiation, and its use
DE10215858A1 (en) * 2002-04-10 2004-03-18 Mnemoscience Gmbh Process for hair treatment with shape memory polymers
BR0304411A (en) * 2002-04-10 2004-07-27 Mnemoscience Gmbh Process for producing impression memory effects on hair by combining impression memory polymers with cationative active substances
US20040091445A1 (en) * 2002-11-01 2004-05-13 The Procter & Gamble Company Rinse-off personal care compositions comprising cationic perfume polymeric particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03084490A1 *

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