EP1648393A1 - Method for producing shape memory effects in hair - Google Patents

Method for producing shape memory effects in hair

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Publication number
EP1648393A1
EP1648393A1 EP20040741009 EP04741009A EP1648393A1 EP 1648393 A1 EP1648393 A1 EP 1648393A1 EP 20040741009 EP20040741009 EP 20040741009 EP 04741009 A EP04741009 A EP 04741009A EP 1648393 A1 EP1648393 A1 EP 1648393A1
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EP
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Patent type
Prior art keywords
hair
shape
shape memory
characterized
composition
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Withdrawn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
EP20040741009
Other languages
German (de)
French (fr)
Inventor
Abdullah Hasson Tareq Ali
Andreas Lendlein
Karl Kratz
Leonid Kuper
Thomas Krause
Axel Kalbfleisch
Anja Duchscherer
Angelika Beyer
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MnemoScience GmbH
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MnemoScience GmbH
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Publication date

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/891Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/892Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a hydroxy group, e.g. dimethiconol
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties

Abstract

The invention relates to a method for producing a retrievable hair restyling. To this end, a composition is applied on the hair (5), said composition containing at least one active ingredient or an active ingredient mixture which can provide a shape memory effect by itself or in combination with other substances after being applied to the hair and after performing the inventive treatment of the hair. The composition additionally contains at least a second active ingredient, namely a hydrophobic substance with a water solubility of = 5 percent by weight at 20 °C. The hair is arranged in a given (permanent) shape and said permanent shaped is then fixed by inducing a chemical or physical modification of the applied active ingredients, wherein after a wanted or unwanted deformation of the shape memory, the original shape memory can be restored by means of a physical simulation. In addition to the permanent hairstyle, a second (temporary) shape can be styled. The invention also relates to a method for restoring a previously programmed permanent hairstyle that can be transformed into a temporary shape or was deformed.

Description

PROCESS FOR PRODUCING FORMGEDACHTNISEFFEKTEN ON HAIR

The present invention is a method for obtaining a retrievable hair forming under use of combinations of hydrophobic active ingredients and active ingredients that give the hair a shape memory effect, in particular the shape memory polymers or crosslinked to shape memory polymers macromers.

In the shaping of hair hair shaping distinction is generally between temporary and permanent, permanent. A temporary hair shaping is generally carried out using compositions based on solutions or dispersions hair-setting polymers. Such products give the hair by the addition of polymer more or less hold, volume, elasticity, bounce and shine. This e styling products such ease. B. as a gel shaping and creating the hairstyle, better than hair spray the status of a hairstyle created and increase as

Festigerschaum the volume of hair. A disadvantage is the s are the gewüns Want effects only of relatively short duration and will be lost due to external influences such as combing, wind, high humidity and contact with water quickly. A permanent hair shaping is usually done by a permanent wave treatment. Here disulfide bonds are reductively cleaved in the hair, put the hair in the new form and fixed by oxidative formation of new disulfide bonds. The disadvantage is that with by the required chemical treatment of hair

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

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

The the present object underlying the invention was to provide compositions with improved efficacy and performance in terms of a retrievable hair styling with a high degree of recovery of a programmed hairstyle form. Improved efficiency and performance can, for example etc improved adhesion to the hair, improved durability of the effect, higher recovery levels of a programmed hairstyle. be. Another object was to make available a process with which it is possible to achieve permanent hair restyling without damaging intervention in the hair structure. Another object was to make available a process which allows to make temporary transformations multiply easily reversed and started with high accuracy to a previously programmed permanent hairstyle. Another object was to make available a process which allows to make due in a simple manner and with high accuracy to external influences deformations of a hairstyle reversed and started to a previously programmed permanent hairstyle.

The object is achieved by a method for Haarbehand- lung, wherein

- a drug composition is applied to the hair, wherein the drug composition (A) contains at least a first active agent or the first active substance complex, which are selected and are formed from materials which are alone or in combination with other substances in a position after application to to give hair and after performing the treatment described below the hair a shape memory effect, and (B) at least one second active ingredient which is selected from hydrophobic materials; the hair before, simultaneously or after application of the active compound composition in a specific form (permanent memory shape) is brought and - then the memory shape is fixed by inducing a chemical or physical change of the applied active ingredients; wherein, after a desired or undesired deformation of the shape memory, the original memory shape is recoverable by a physical stimulation substantially. Hydrophobic substances within the meaning of the invention are substances with a water solubility of <5 wt.%, Preferably <2 wt.% At 20 ° C. The weight ratio of (A): (B) may, for example from 1: 100 to 1000: 1, from 1:50 to 200: 1, from 1:10 to 5: 1, or from 1: 1 to 2.5: 1 respectively.

One embodiment relates to a method of treating hair using an active ingredient composition in the at least two substances are included, which individually have no or only weak shape memory properties and confers, when used together according to the method hair a synergistically increased shape memory effect. Here, the at least two materials may comprise either the above first active ingredient and the above-mentioned hydrophobic second active ingredient or at least two materials forming the Wirkstoffkomple above.

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

- the first active ingredient of the applied to the hair composition is a crosslinkable macromer forming a shape memory polymer after cross-linking, wherein the macromer a) contains cross-linkable regions that are cross-linkable through chemical bonds and b) thermoplastic regions that are not chemically cross-linkable,

- before, simultaneously or subsequently the hair is brought into a specific (continuous) form, and then the shape is fixed by chemical crosslinking of the macromer to form the shape memory polymer, wherein the shape memory polymer comprises at least one transition temperature T trans.

Another object of the invention is a method for impressing a second hair style over a programmed, retrievable first hairstyle. In this case, a programmed by the above method is first heated hairstyle (permanent shape) to a temperature above Tt r a ns. The hair is then placed in the desired second form (temporary) and the second shape is fixed by cooling to a temperature below T trans.

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

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

reconvert force by simple heating or by other energetic stimulus. Deformation and reconversion (recovery) are multiple possible. The degree of achievement of the original, permanent shape is somewhat lower than in subsequent cycles in a first relaxation cycle consisting of deformation and reconversion, usually, is probably due to the elimination of initially still present imperfections, textures etc .. A particularly high degree of recovery but then achieved in the subsequent relaxation. The degree of recovery is in the first relaxation preferably at least 30%, more preferably at least 40% and in the subsequent relaxation preferably at least 40%, more preferably at least 50%. but it may also be 75%, 90% or more. The degree of recovery can be measured as in the conventional curl retention measurements by simple length of a treated hair tress, or by known suitable train-strain experiments. The shape memory effect of hair is the property that a particular hairstyle (permanent shape memory) can be restored after deformation spontaneously and without external force by simple heating or by another energy stimulus substantially, ie, at a first relaxation to preferably at least 30 %, particularly preferably at least 40% and in the subsequent relaxation is preferably at least 40%, more preferably at least 50% or 75%.

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

According to the invention suitable shape memory polymers have at least one transition temperature T trans. These may be a melting temperature T m or a glass transition temperature T g. Above T trans, the

Polymer has a lower modulus of elasticity than below T trans - lower the ratio of the elasticity modules and above T trans is preferably at least 20. The transition temperature r a n s is preferably greater than room temperature-temperature (20 ° C), especially at least 30 ° C, more preferably at least 40 ° C and is the temperature above which the spontaneous recovery of the permanent shape from the deformed or from the temporary mold.

Hairstyle or hairstyle according to the invention has a broad meaning and comprises, for example, the degree of curl or the degree of smoothness of hair. A programmed hairstyle according to the invention is a collection of hair that have cross-linked by and fixed in a permanent shape, shape memory polymers, a certain shape. Restoring a programmed hairstyle in the sense of the invention means that the programmed hairstyle regresses after deformation again preferably at least 40%, more preferably at least 50% or 60%, based on the shape which results after a first relaxation. The degree of recovery can be effected for example by length measurement of a lock of hair or a hair strand.

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

Basically suitable are all synthetic or natural oligomers and polymers having reactive end or side groups which the crosslinked polymer has an adequate memory From

Transition temperature Ttrans un above <3- appropriate modules of elasticity and impart below Ttrans and wherein the end or side groups either during manufacture or subsequently by derivatization are present in a reactive form, which allow a crosslinking reaction with the above mentioned methods. Suitable macromers are those of the general formula Al (X) n -A2 (I) wherein Al and A2 represent reactive, chemically cross-linkable groups and - (X) n- represents a divalent, thermoplastic polymer or oligomer. Al and A2 are preferably acrylate or methacrylate groups. The segment (X) n is preferably polyester, oligoester, polyalkylene glycol, Oligoalkylenglykol-,

Polyalkylencarbonat- and Oligoalkylencarbonatsegmente, where the alkylene groups are preferably ethylene or propylene groups. Suitable macromonomers to form thermoset polymers with shape memory properties are oligo- or poly (ε-caprolactone), oligo- or polylactides, oligo- or

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

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

Suitable synthetic polymer blocks are polyphosphazenes, poly (vinyl alcohole), polyamides, polyesteramides, polyaminoacids, polyanhydrides, polycarbonates, poly (lactide-co-glycolides), polyacrylates, polyalkylenes, polyacrylamides, polyalkylene glycols, polyalkylene oxides, polyalkylene terephthalates, polyortho esters, polyvinyl ethers, polyvinyl esters, polyvinyl halides , polyvinylpyrrolidone, polyesters, polylactides, polyglycolides, polysiloxanes, polyurethanes and copolymers thereof. Examples of suitable polyacrylates include poly (methyl methacrylate), poly (ethyl methacrylate), poly (butyl methacrylate),

Poly (isobutyl methacrylate), poly (hexyl methacrylate), poly (isodecyl methacrylate), poly (lauryl methacrylate), poly (phenyl methacrylate), poly (methyl acrylate), poly (isopropyl acrylate), poly (isobutyl acrylate) or poly (octadecyl acrylate). Suitable synthethische, easily biodegradable polymer segments are polyhydroxy acids such as polylactides, polyglycolides and copolymers thereof, poly (ethylene terephthalate); Poly (hydroxybutyric acid); Poly (hydroxyvaleric acid); Poly [lactide-co- (ε-caprolactone)], - poly [glycolide-co- (ε-caprolactone)]; Polycarbonates, poly (amino acids); Poly (hydroxyalkanoates); polyanhydrides; Polyorthoesters as well as their mixtures and copolymers. Examples of poor biodegradable polymer segments are poly (methacrylic acid), poly (acrylic acid), polyamides, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylphenol, and copolymers and mixtures thereof.

In a particularly preferred embodiment, the composition comprises a mixture of (AI) macromers which are substituted with at least two reactive, crosslinkable groups, and (A2) macromers which are substituted with only one reactive group. Suitable additional macromers z. B. those of the general formula R- (X ') n "A3 (II) wherein R represents a monovalent organic residue, A3 designates a reactive, chemically cross-linkable group and - (X' n) represents a divalent, thermoplastic polymer or oligomer segment . A3 is preferably an acrylate or methacrylate. the segment (X ') n is preferably polyalkylene glycols, the monoalkyl ethers and their copolymers, wherein the alkylene groups are preferably ethylene or propylene and the alkyl groups have preferably 1 to 30 carbon atoms. particularly preferred are mixtures of (AI) terminal at both ends with acrylic or methacrylic acid esterified polyalkylene glycols or polycaprolactones and (A2) terminal at one end with acrylic or methacrylic acid esterified polyalkylene glycol monoalkyl ethers, wherein the alkylene groups are preferably ethylene or propylene groups and the alkyl groups preferably Cl- are to C30 alkyl groups. As the component (AI), the einsetzb alone Ar is are preferred: Poly (ε-caprolactone) dimethacrylate, poly (DL-lactide) dimethacrylate, poly (L-lactide-co-glycolide) - dimethacrylate, poly (ethylene glycol) dimethacrylate,

Poly (propylene glycol) dimethacrylate, PEG-block-PPG-PEG block-dimethacrylate, poly (ethylene adipate) dimethacrylate, hexamethylene dimethacrylate. As the component (B) are for example suitable: poly (ethylene glycol) monoacrylate,

Pol (propylene glycol) monoacrylate and their monoalkyl ethers.

A further particular embodiment relates to a method for hair treatment, wherein

- the first active ingredient of the applied to the hair composition is a shape memory polymer which comprises at least two transition temperatures Tt rans and T 'trans, and a) at least one crosslinkable by physical interaction hard segment having a first transition temperature T' trans / - The 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 lower than T 'trans, preferably at least 10 ° C below T' trans, - before, simultaneously or subsequently, the hair is brought into a specific (continuous) form, and - then the shape is fixed by physical crosslinking of the shape memory polymers.

The shaping of the hair is conveniently effected with heating to a temperature of at least T 'trans and the hair shape is formed by cooling to a temperature below' fixed trans. usually, room temperature means the ambient temperature is preferably at least 20 ° C, in warmer climates, preferably at least 25 ° C. The application of the composition to the hair may be done in verschiedenene ways, for example directly by spraying or indirectly by applying first to the hand or a suitable device such. B. comb, brush, etc., and then distributing in or on the hair. The consistency of the composition can for example be that of a solution, dispersion, lotion, thickened lotion, gel, foam, a semi-solid, cream-like or waxy.

Another object of the invention is a method for on rägung a second hair style over a programmed, retrievable first hairstyle. In this case, a programmed by the above method is first hairstyle (permanent shape) is heated to a temperature between T 'and T trans tran s. The hair is then placed in the desired second form (temporary) and the second shape is fixed by cooling to a temperature below T tas.

Another object of the invention is a process for the recovery of a previously programmed by the above method first hairstyle (permanent

Shape) . For this purpose, a hairstyle in a temporary shape or a deformed by cold deformation of hair to a temperature above T tran s is heated. The permanent shape forms a spur and back automatically. Cold-forming of a hair style is a style alteration at ambient temperature to understand without the supply of additional heat by a hair dryer or similar devices. The deformation may here be mechanically caused, for example, by simply dismantling of the curls under the action of gravity, by combing or brushing of hair, by wind or humidity, due to mechanical influences during sleep or chaise longue etc ..

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

Physically crosslinkable shape memory polymers in the sense of the invention are polymers in which the fixation of the impressed permanent shape is made by cross-linking due to physical interactions. Cross-linking by physical interactions can be achieved that certain segments of the polymer chains associate into crystalline domains. The physical interactions, it can transfer to batch Complex to hydrogen bonds, dipolar or hydrophobic interactions to act van der Waals interactions or ionic interactions of Polyelektrolytsegmenten. The interaction may take place between different segments within a polymer strand (intramolecular) and / or between different polymer strands (intermolecular). The formation of the interactions may be triggered for example by cooling (in particular in the case of crystallization) and / or by drying, that is by removal of solvents.

According to the invention suitable physically crosslinkable shape memory polymers contain at least two transition temperatures T s and ran T'ta n s. The two transition temperatures, it may for example be melting temperatures T m or glass transition temperatures Tg. Above T trans, the polymer has a lower modulus of elasticity than below Ttrans- The ratio of the moduli of elasticity below and above T trans, s is preferably at least 10, more preferably at least 20. The lower transition temperature T tr a n s is preferably greater than room temperature (20 ° C), especially at least 30 ° C, more preferably at least 35 ° C or at least 40 ° C and is the temperature above which the spontaneous recovery of the permanent shape from the deformed or from the temporary mold. T trans is preferably as far as above the usually expected ambient temperatures is that at ambient temperature no significant unintended, thermally induced deformation of the temporary shape occurs. Suitable ranges for T tran s are, for example from 25 to 100 ° C, from 30 to 75 ° C, 35 to 70 ° C or from 40 to 60 ° C. The upper transition temperature T 'trans is greater than Tt r a ns and is the temperature above which the impressing of the permanent shape or reshaping a permanent shape takes place in a new permanent mold, and below which the permanent shape is fixed. T 'trans is preferably as far as above T transr that upon heating the hair to a temperature above T rans to recover the permanent shape or to rebuild a temporary hairstyle while maintaining the permanent hairstyle no significant unintended, thermally induced deformation of the permanent shape occurs.

Preferably T'T r a n s of at least 10 ° C, more preferably at least 20 ° c or at least 30 ° C above train path, the difference between T 'trans and T tr ans, for example, from 10 to 80 ° C, from 20 to be 70 ° C or from 30 to 60 ° C. Suitable ranges for T 'trans are, for example from 40 to 150 ° C, of 50 to 100 ° C or from 70 to 95 ° C.

Suitable physically cross-linked shape memory polymers are polymers which at least consist of a hard segment and at least one soft segment. The hard segment includes physical crosslinks and has a transition temperature T 't ans, the above room temperature, preferably more than 10 ° C above 20 ° C. The soft segment has a transition temperature T tr which below T'T s ran, preferably at least 10 ° C below T 'trans ans /. The polymer segments are preferably oligomers, particularly linear chain molecules with a molecular weight of for example, 400 to 30,000, preferably 1,000 to 20,000 or 1,500 to 15,000. It may be linear di-, tri-, tetra- or multiblock copolymers, branched, acting dendritic or grafted copolymers. Preferably, it is not linear polyether urethanes containing bis (2-hydroxy-ethyl) hydroquinone. The molecular weight of the polymers may be for example 30,000 to 1,000,000, preferably 50,000 to 700,000 or 70,000 to 400,000. Suitable physically cross-linked shape memory polymers are described in WO 99/42147 and are referred to therein as thermoplastic polymers. The thermoplastic polymers and the preparation methods described in WO 99/42147 described therein are suitable according to the invention and part of this application. They have a degree of crystallinity of preferably 3 to 80%, particularly preferably from 3 to 60%. The ratio of the moduli of elasticity below and above T trans is-half of preferably at least 10, more preferably at least twentieth The polymer segments may be of natural polymers such. B. acting proteins or polysaccharides derived segments. It can also be synthetic polymer blocks themselves. 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 a first type of blocks and at least one different second type of blocks, the blocks cause the multiblock copolymer two different transition temperatures eist. Suitable multi-block copolymers are in particular those which are prepared from at least two different macrodiols and at least one diisocyanate. Macrodiols are oligomers or polymers having at least two free hydroxyl groups. Oligomers are usually at least two, preferably at least three, in particular 4 to 20, 5 to 15 or 6 to 10 monomers. The macrodiols may have the general formula HO-A-OH wherein A represents a divalent, oligomeric or polymeric group, preferably polyester or oligoesters. The diisocyanate may have the general formula OCN-B-NCO, in which B represents a divalent organic group, preferably an alkylene or

Arylene group which may be substituted by further substituents. The alkylene group may be linear, branched or cyclic and preferably has 1 to 30 carbon atoms, more preferably 2 to 20 or 5 to 15 carbon atoms.

Particularly preferred shape memory polymers are the copolyester urethanes described in WO 99/42147, in particular the reaction products of (a) two different macrodiols selected from α, ω-dihydroxy-polyesters, α, oligoesters ω-dihydroxy-, ω-dihydroxy polylactones and α, ω-dihydroxy oligolactones and (b) at least one diisocyanate, preferably trimethylhexane-1, 6-diisocyanate. Particularly preferred are macrodiols of 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 of 400 to 30,000, preferably 1,000 to 20,000, or preferably from 1500 to 15000. The molecular weight of the multiblock copolymers resultiernden M w = 30,000 to 1,000,000, more preferably 50,000 to 700,000 or 70,000 to 400,000 g / mol, determined by GPC. The polydispersities are preferably in the range from 1.7 to 2.0.

Hydrophobic drugs Suitable hydrophobic agents include oils, fats, waxes, fatty alcohols, fatty acids, hydrophobic polymers, hydrophobic surfactants, hydrophobic silicone compounds etc. Suitable hydrophobic surfactants are in particular those having HLB values ​​<7, for example, ethoxylated C8 to C30, preferably CIO-C20 fatty alcohols with a

Degree of ethoxylation of preferably 1, 2 or 3, for example, Ceteareth-2, Ceteareth-3, Ceteth-1, Ceteth-2, Ceteth-3, laureth-1, laureth-2, laureth-3, Myreth-2, Myreth-3, oleth-2, oleth-3, steareth-2, steareth-third Suitable oils include those having a melting point below 25 ° C and a boiling point of preferably greater than

250 ° C, in particular above 300 ° C. Questioned vegetable or animal oils, mineral oils (liquid paraffin), oil-like fatty acid ester or Fettalkoholester come. Also suitable are hydrocarbon oils such as paraffin or isoparaffin, squalane, oils from fatty acids and polyols, especially triglycerides. Suitable vegetable oils include sunflower oil, coconut oil, castor oil, lanolin oil, jojoba oil, corn oil, soybean oil. Suitable waxes include animal, vegetable, mineral and synthetic waxes, microcrystalline waxes, macrocrystalline waxes, solid paraffins, ozocerite, montan wax, Fischer-Tropsch waxes,

Polyolefin such as polybutene, beeswax, wool wax and its derivatives, such as wool wax alcohols, candelilla wax, carnauba wax, Japan wax, hardened fats, fatty acid ester and fatty acid glycerides with a solidification point of in each case above 40 ° C, wax alcohols, wax acids, and polyethylene waxes etc. have a The waxes or waxy substances solidification point above 40 ° C, preferably above 55 ° C. Suitable hydrophobic soft waxy substances are, for example petroleum jelly or semi-solid paraffins, for example petroleum jelly (semi-solid mixture of hydrocarbons derived from petroleum). The

Solidification points are usually in the range of about 25 ° C to 40 ° C. Hydrophobic polymers are preferably selected from polymers which contain at least one monomer, which is selected from Acrylsaurealkylestern Methacrylsäurealkylestem and wherein the alkyl groups of at least 6 carbon atoms, preferably 8 to 30 carbon atoms.

Hydrophobic silicone compounds are preferably selected from silicone oils, silicone waxes, dimethylpolysiloxanes and dimethylsiloxane / alkylmethylsiloxane copolymers wherein the alkyl groups of at least 6 carbon atoms, preferably 8 to 30 carbon atoms. Suitable silicone compounds are, for example, silicone waxes, polydimethylsiloxane (dimethicone), phenylated silicones, polyphenylmethylsiloxanes, phenyltrimethicones, methylpolysiloxanes having alkyl side chains wherein the alkyl groups of 2 to 30, preferably at least 8 carbon atoms, particularly preferably having 10 to 20 carbon atoms (such as stearyl dimethicone) ,-hydro-ω- hydroxypolyoxydimethylsilylen (Dimethiconol), cyclic dimethylpolysiloxane (cyclomethicone), trimethyl (octadecyloxy) silane (stearoxytrimethylsilane), dimethylsiloxane / glycol copolymer (dimethicone copolyol), dimethylsiloxane / aminoalkylsiloxane copolymer having hydroxyl end groups (amodimethicone), monomethylpolysiloxane with Laurylseitenketten and polyoxyethylene - and / or polyoxyethylene propylenendketten (lauryl methicone copolyol), dimethylsiloxane / glycol Copolymeracetat (dimethicone copolyol acetate), dimethylsiloxane / aminoalkylsiloxane copolymer with trimethyl silyl (trimethyl). Preferred silicone polymers are dimethicone, cyclomethicone and Dimethi- Conole. Mixtures of silicone polymers are suitable, such as a mixture of dimethicone and dimethiconol. The names given above in parentheses correspond to the INCI nomenclature (International Cosmetic Ingredients), as they are intended for labeling of cosmetic active ingredients and excipients. Particularly preferred hydrophobic materials are dimer acids and their derivatives. Dimer acids are dimerisserte fatty acids, particularly the dimers of mono-unsaturated C8 to C30 fatty acids, eg oleic acid or tall oil acid (TOFA). Derivatives are, for example, dimer diol, and Dimerdiololigoether oligoester. Dimer diol is the name, ω-C36-diols that may be prepared by dimerization of oleyl alcohol or by hydrogenation of dimer fatty acids or esters thereof. Oligoester may be prepared by acid-catalyzed dehydration of dimer diol. Oligoester are the dihydroxyesters from dicarboxylic acids and diols fat-based. The molecular weight of the oligoester diols Dimerdiololigoether and is preferably about 1,000 to 10,000, more preferably about 2000 to about 5000. Preferred oligomers are in particular dimers, trimers and tetramers. Preferred commercially available diols are dimer diols (Sovermol ® 908, Cognis, molecular weight ca.550 g / mol) and Dimerdiololigoether (Sovermol 909 ®, molecular weight ca. 1000 g / mol and Sovermol 910 ®, molecular weight ca. 2000 g / mol).

The hydrophobic ingredients, it may be low-volatile or highly volatile substances, heavy volatile strength, on the hair remaining materials are preferred, especially those having an evaporation number of preferably greater than 20, more preferably greater than 100. The evaporation number is defined as the quotient of the evaporation time of the liquid to be tested and the evaporation time of diethylether as a comparative liquid. In a preferred embodiment, the hair treatment composition of the invention contains both at least one difficultly volatile hydrophobic substance and at least one volatile hydrophobic substance having an evaporation number of less than 20th

Compositions of the invention for the treatment of hair containing the first, by weight a shape memory effect of hair alone or in combination with another substance causing agent in an amount of preferably 0.01 to 25%., Particularly preferably from 0.1 to 15 wt.% In a suitable medium. Preferred amounts of the hydrophobic active ingredients are present from 0.01 to 10.%, Particularly preferably from 0.05 to 5 wt.%. The composition may, inter alia, present as a solution, dispersion, emulsion, suspension, or latex. The liquid, gel, semi-solid or solid medium is substantially cosmetically acceptable and physiologically harmless.

The composition of the invention is generally a solution or dispersion in a suitable Lösungsbzw. Dispersants before. Particularly preferred Video- water, organic solvents and mixtures of water and. at least one organic solvent. Preferred organic solvents include alcohols and acetone. Suitable solvents are aliphatic linear or branched Cl to C4 alcohols or a mixture of water with one of these alcohols. However, it can also be used other organic solvents, in particular straight or branched

Hydrocarbons such as pentane, hexane, isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane, organic linear or cyclic ethers, for example tetrahydrofuran (THF) or liquid organic esters such as ethyl acetate may be mentioned. Further, suitable solvents are silicone based, especially silicone oils based on linear or cyclic polydimethylsiloxanes (Dimethicone or Cyclomethicone). wherein preferred are volatile silicones having a boiling point less than 200 ° C. Further solvents are acetone, tetrahydrofuran, chloroform, etc. The solvents are preferably present in an amount of 0.5 to 99 wt.%, Particularly preferably in an amount of 10 to 97 wt.%, From 20 to 95 wt.%, Or from 40 to 90 wt.% before.

Compositions of the invention may additionally 0.01 to 25 wt.% Containing at least one hair-care, hair-setting and / or hair-coloring agent. Hair setting agents are in particular the known conventional film-forming and hair-setting polymers. have the film-forming and hair-fixing polymer can see synthetic or natural origin and non-ionic, cationic, anionic or amphoteric character. Such a polymeric additive is present in amounts of 0.01 to 25th%, preferably 0.1 to 20th%, particularly preferably from 0.5 to 15 °.% May be contained, may also consist of a mixture of several Polymerern exist and are modified by the addition of other polymers with a thickening effect in its hair-setting properties. Among film-forming, hair-setting polymers, such polymers are understood according to the invention, which when used in 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a polymer film on the hair and strengthen this way the hair ,

Suitable synthetic, nonionic film-forming, hair-fixing polymers may be used in the inventive hair treatment agent, homopolymers of vinyl pyrrolidone, homopolymers of N-vinylformamide, copoly erisate of vinylpyrrolidone and vinyl acetate, terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate;

Polyacrylamides, polyvinyl alcohols, or polyethylene glycols having a molecular weight of 800 to 20,000 g / mol. Among the suitable synthetic film-forming anionic polymers are crotonic acid / vinyl acetate copolymers and terpolymers of acrylic acid, ethyl acrylate and Nt-butylacrylamide. Natural film-forming polymers or polymers produced therefrom by chemical conversion may also be employed in the inventive hair treatment compositions, for example, Chinese balsam resin, cellulose derivatives such as hydroxypropyl cellulose having a molecular weight of 30,000 to 50,000 g / mol, or shellac in neutralized or unneutralized form. Amphoteric polymers may also in the present

Hair treatment agents are used. Suitable z. For example, copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers from the group of acrylic acid, methacrylic acid and simple esters thereof.

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

An inventive cosmetic composition can be applied in various application forms, such as in the form of a lotion, a spray lotion, a cream, a gel, a Gelschaums, an aerosol spray, a nonaerosol spray, aerosol foam, a non-aerosol foam, an O / W - or W / O emulsion, a microemulsion or a hair wax.

When the hair treatment composition of the invention is in the form of an aerosol spray it additionally contains 15 to 85 wt.%, Preferably 25 to 75 wt.% Of a propellant and is bottled in a pressurized container with a spray head. As a blowing agent, lower alkanes, such as n-butane, isobutane and propane, or also their mixtures as well as dimethyl ether or fluorohydrocarbons such as F 152a (1, 1-difluoroethane) or F 134 (tetrafluoroethane) as well as also at the pressures in question in gaseous form suitable the aforementioned propellants propellants, such as N2, N2O and CO2 as well as mixtures.

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

When the hair treatment composition of the invention is in the form of a hair foam (mousse), it contains at least one customary foam-imparting substance known for this purpose. The composition is foamed with or without the aid of propellant gases or chemical propellants and worked as a foam into the hair and left in the hair without rinsing. A product of the invention comprises a device for foaming the composition as an additional component. Devices for foaming are understood to be those devices which enable the foaming of a liquid with or without use of a propellant. A suitable mechanical foaming device, for example, a commercially available foam pump or an aerosol foam head can be used.

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

When the hair treatment composition of the invention is in the form of a hair wax, it contains water-insoluble fat or wax substances or substances in an amount to provide the composition with a waxy consistency, preferably 0.5 to 30 wt .-%. Suitable water-insoluble substances are, for example, emulsifiers having an HLB value below 7, silicone oils, silicone waxes, waxes (for example, wax alcohols, wax acids, wax Sesterheim, and in particular natural waxes such as beeswax, carnauba wax, etc.), fatty alcohols, fatty acids, fatty acid ester or high molecular weight polyethylene glycols a molecular weight of 800 to 20,000, preferably from 2,000 to 10,000 g / mol.

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

Hair lotion, it is present as a non-viscous or low-viscous, flowable essentially solution, dispersion or emulsion with a content of at least 10 wt.%, Preferably 20 to 95 wt.% Of a cosmetically compatible alcohol. As alcohols, particularly the lower Cl commonly used for cosmetic purposes can be used to C4 alcohols such as ethanol and isopropanol. When the hair treatment composition of the invention is in the form of a hair cream, it is preferably present as an emulsion and comprises either additionally viscosity-imparting ingredients in an amount of 0, 1 to 10 wt.% Or the required viscosity and creamy consistency is built up through micelle formation with the aid of suitable emulsifiers , fatty acids, fatty alcohols, waxes, et c. constructed in a conventional manner.

In a preferred embodiment, the inventive composition capable of gleizeitig to allow both the impressing a retrievable hair and a hair dyeing. The agent is then as a coloring hair treatment agents such. B. etc as dye fixatives, dye cream, coloring foam. formulated. It then contains at least a colorant. These may be organic dyes, in particular so-called direktziehnde dyes or also inorganic pigments. The total amount of dyes is in the invention means about 0 wt 01-7.%, Preferably about 0, 2 to 4 wt.%. suitable for the agents of the invention direct dyes are, for example Triphenylmethanfarbstof fe, fe aromatic Nitrofarbstof, azo dyes, Chinonfarbstof fe, cationic or anionic dyes.

Suitable hair-coloring pigments are practically insoluble colorants in the application medium and can be inorganic or organic. Also inorganic-organic mixed pigments are possible. The pigments are preferably not igmente Nano. The preferred particle size is 1 to 200 microns, particularly 3 to 150 microns, more preferably 10 to 100 μm.Bevorzugt are inorganic pigments. The 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 of 0, 05 by weight to the fifth %. Preferred hair conditioning agents are cationic agents. Cation-active substances are characterized in that they carry either at least one permanent cationic group in the molecule, z. B. an iminium group or an ammonium group, in particular a quaternary ammonium group or that they carry at least one group which is kationisierbar, e .g. a primary, secondary or tertiary amine group, which is kationisierbar by protonation, said quaternary ammonium groups are preferred. The cation-active agent is a substance which, due to the cationic or cationizable group is a substantivity to human hair. Suitable cation-active substances are,. B. Surfactants with cationic or cationizable groups, especially cationic surfactants, betaine or amphoteric surfactants; Polymers with cationic or cationizable groups, especially cationic, betainic or amphoteric polymers; Silicone compounds with cationic or cationizable groups, especially diquaternary or polyquaternary siloxanes or amodimethicones; cationically derivatized proteins; cationically derivatized protein hydrolysates or betaine.

Usually medium more known cosmetic additives can be added to the hair treatment according to the invention, eg. B. non-fixing, nonionic polymers such as polyethylene glycols, non-fixing, anionic and natural polymers and mixtures thereof in an amount of preferably 0 to 01 wt 50th %. Also, perfume oils and fragrances in an amount of 0, 01 by weight to the fifth %

Opacifiers such as ethylene glycol distearate in an amount of 0, 01 by weight to the fifth %, Wetting or emulsifying agents, in particular anionic or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, fatty acid alkanolamides, such as the esters of hydrogenated castor oil is present in an amount of 0.1 to 30th%, further humectants, tinting agents, light stabilizers, antioxidants and preservatives in an amount by weight of 0.01 to 10.%.

Figure 1 schematically shows a possible method for producing a triggerable permanent shape. A strand of hair is wound on a bobbin and sprayed with a present invention, a cross-linkable macromer-containing solution. the desired permanent shape is fixed by irradiation with a suitable energy source, such as a UV lamp. Finally, the winding body is removed. Figure 2 shows the deformation of a permanent shape and recovery of the permanent shape from the temporary shape. The lock of hair in the permanent shape has the length lo - The curl in the deformed shape has the length l. The curl in the recovered shape has length I2 • The degree of recovery (recovery) calculated as follows: Recovery = d - 12) / di - io).

As a measure for assessing the shape memory properties of a composition of the memory factor can be used, in which both the formability of a permanent hairstyle into a temporary shape (form factor) as well as the recovery of the permanent shape from the temporary shape (restoration factor, degree of recovery) are considered. It is assumed that a smooth streak to a curly shape has been impressed as a permanent shape and then a second, smooth shape has been impressed as a temporary shape to, the form factor can be determined according to the following criteria:

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

The memory factor M results from the respective shape factor f, the maximum shape factor F = 4, the respective reset factor r and the maximum restoration factor R = 6 according to M = (f / F) * (r / R) * 100 The Memory factor should ideally not be less than 25, preferably between 25 and 33.3, more preferably between 37 and 100. the following examples are intended to illustrate the invention in more detail.

Examples

Examples 1-12 Compositions are prepared according to Table 1 (amounts in g). Table 1

Methacrylic acid esterified 2 'α, ω-C36-diol (Cognis) 3 ^ oligomer of dimer diol "(Cognis) ^' synthetic oligoester diol of dicarboxylic acids and diols fat-based 'Like' terminally esterified with methacrylic 'Like' terminally esterified with methacrylic acid 7 'As ^' terminally esterified with methacrylic acid

a product of Aldrich 10) Castoryl maleates, a product of ISP 'Stearyl Dimethicone, a Propdukt Clariant

The memory M factor is determined according to the method described above.

For the preparation of the permanent shape a wetted with water streak a length of 20 cm is turned to a hair curler and the polymer solution applied (20-30 mg polymer / g hair). The treated tress is fixed at 70 ° C for 30 minutes under UV light. After cooling to about 25 ° C the hair curler is eliminator. The curled strand (impressed permanent shape) had a length of about 4.5 cm. For fabricating the temporary shape (for example, smooth) the curled strand is heated to about 55 ° C, stretched to their original, full length (20 cm) and cooled to room temperature. For the recovery of the permanent shape of the smooth strand is heated to about 55 ° C. The tress retired at this temperature spontaneously together to the permanent shape (curly). To re of the permanent shape (for example, smooth) the curled strand is heated again to 55 ° C, to its full length (20 cm) stretched and cooled to room temperature.

Examples of the crosslinkable macromer in the following hair treatment agents, the following can be crosslinked to shape memory polymers macromers are used. The preparation of the macromer is carried out analogously as described in WO 99/42147 described. Ml PEG (4k) -DMA, polyethylene glycol with molecular weight of about 4000, two times with methacrylic acid esterified M2 PEG (8k) -DMA, polyethylene glycol with molecular weight of about 8000, two times with methacrylic acid esterified M3 PEG (LOC) -DMA, polyethylene glycol having molecular weight of about 10000, M4 doubly esterified with methacrylic PLGA (7k) -DMA, poly (L-lactide-cσ-glycolide) dimethacrylate having a molecular weight of about 7000 M5 PCI (10k) -DMA, poly (ε-caprolactone) dimethacrylate having a molecular weight of approximately 10,000

The application of the following hair treatment composition was as described, with similar results as in Example. 1

Example 13: nonaerosol spray 5.0 g macromer Ml 0.5 g of PVP / VA copolymer 0.5 g Luviquat ® FC 550 3) 0.5 g Tetraethoxylaurylether 1 g of dimethylpolysiloxane (Wacker-Belsil ® DM 500) 0.5 g Polysorbate 40 100 g ethanol ad '40% solution of methylvinylimidazolium chloride / vinylpyrrolidone copolymer (Polyquaternium-lS) in water

The lotion is sprayed by means of a commercially available spray pump directly on dry or damp hair.

Example 14: liquid setting with memory effect 6.0 g of macromer M2 5.0 g of cyclo-octamethyltetrasiloxane 5.0 g vinylpyrrolidone / vinylacetate copolymer 2.0 g dihydroxy polydimethylsiloxane, 12% in cyclodimethylsiloxane (Abil OSW 12 from Goldschmidt / Germany) ad 100 g pentane

Example 15: Hair wax shape memory 7 g macromer M3 6 g Ethanol 4 g cetyl alcohol 4 g Petrolatum 3 g 3 g Carnauba Wax Ceresin 2 g Ceteareth-25 2 g Polyvinylpyrrolidone 1.5 g Mineral oil 1.5 g dicaprylyl maleate 0.5 g Carbomer 0, 4 g aminomethylpropanol ad 100 g water

Example 16 i hair fluid with memory effect 3 g macromer M4 0.6 g Behenyltrimethylammonium chloride 0.5 g Sunflower oil 0.5 g of dimethylpolysiloxane (Wacker-Belsil ® DM 1000) 0.5 g Abil Quat ® 3272 (Quaternium-80) 0.5 g guar Hydroxypropyltrimonium Chloride 0.5 g panthenol 0.4 g cetearyl alcohol 0.2 g beeswax 0.1 g cetyl alcohol 0.1 g PEG-20 stearate q. s. Preservatives, perfumes, water ad 100 g

Example 17: Aerosol foam shape memory 4 g macromer M5 1 g Dow Corning DC 1401 fluid (Dimethiconol / Cyclomethicone 13/87) 1 g Glucose 0.6 g 0.8 g Polyvinylpyrro1idon Abil Quat ® 3272 (Quaternium-80) 0, 2 g cetyltrimethylammonium chloride 0.2 g Polyquaternium-11 0.2 g of silica 0.1 g Laureth-2 to 100 g water The composition is 5 wt.% bottled propane / butane in a pressure-resistant aerosol packaging with foaming head.

In Examples 14 to 17, the macromer used in each case can be wholly or partly against one of the other macromers Ml to M5 replaced with similar results.

Examples of thermoplastic shape memory polymers

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

The abbreviations of the macrodiols mean: PD: poly (para-dioxanone) PLGA: Poly (L-lactide-co-glycolide) PCL: poly (ε-caprolactone) PDL: poly (pentadecalactone) The numbers in the names of the macrodiols are each the approximate molecular weight of the macrodiols (± 100). The following hair treatment agents are applied as follows: On the hair a sufficient depending on hair length amount of the agent is applied. The hair is brought into the desired form, for example wound on curlers or stretched and dried. The mixture is then heated to about 70 ° C. After cooling to room temperature (about 25 ° C) the curlers are removed. For impressing a second hairstyle (temporary shape) is heated, the first hairstyle to about 55 ° C, into a second hairstyle and cooled to room temperature. When reheated to about 55 ° C, the first hairstyle forms spontaneously.

EXAMPLE 18: Hair cream with the shape memory effect of 5 g of polymer Pl 0.5 g cyclooctamethyltetrasiloxane 2 g of acrylate / alkyl acrylate copolymer (Pemulen ® TR1) 1 9 Abil ® OSW 13 (Dimethiconol, 13% in cyclomethicone) 5 g of water

To 100 g of isopropanol

Example 19: Aerosol foam shape memory 6 g of polymer P2 1 g Dow Corning DC 1401 fluid (Dimethiconol / Cyclomethicone 13/87) 0.2 g Polyvinylpyrrolidone 0.8 g Abil Quat ® 3272 (Quaternium-80) 0.3 g cetyl trimethyl ammonium chloride 0.2 g Polyquaternium-11 0.2 g panthenol 0.1 g jojoba oil, orange peel wax, apple wax shell to 100 g water

The composition is 5 wt.% Bottled propane / butane in a pressure-resistant aerosol packaging with foaming head.

Example 20: Flüssigfarbfestiger with memory effect 4.0g Polymer P7 2.0 g of cyclo-octamethyltetrasiloxane 0.5g Dimethiconol (Silicone Fluid F 212 from Wacker / Germany) 0.07 g l-Amino-4- (2, 3-dihydroxypropyl) amino-5-chloro-2-nitrobenzene 00, 0055 gg Basic Brown 17 (CI 12251) 0, 0023 g of Basic Violet 14 (CI 42595) 0, 01 g Basic Blue 7 (CI 42595) 20 0 g of pentane ad 100 g propanol

Example 21: Hair Spray with memory effect 5, 0 g of polymer P8 0.5 g of cyclo-octamethyltetrasiloxane 0.5 g Dimethiconol (Silicone Fluid F 212 from Wacker / Germany) 5.0 g Vinyl pyrrolidone / vinyl acetate copolymer 35 g of propane / butane ad 100 g pentane

Example 22: Hair wax shape memory polymer P3 8 g 5 g Glyceryl stearate 4 g Cocamide MEA 3 g Ceresin 3 g isopropyl myristate 3 g Triceteareth-4 phosphate 2 g Laureth-4 1 g Ceteareth-25 0.5 g Cetyl trimethylammonium chloride 0.5 g polyvinylpyrrolidone / vinyl acetate copolymer to 100 g of water In the examples 18 to 22 can be used in each case, the

Shape memory polymer in whole or in part to one of the other

Polymers Pl are exchanged to P8 with similar results.

Claims

claims
1. A method for hair treatment, wherein - a drug composition is applied to the hair, wherein the drug composition (A) contains at least one first active agent or the first active substance complex, which are selected or are formed of materials which alone or in combination with other substances in are able to impart a shape memory effect after application to hair, and after performing the treatment described below the hair, and wherein the active substance composition (B) contains at least one second active ingredient which is selected from hydrophobic materials with a water solubility of <5 wt% at 20 ° C. the hair before, simultaneously or after application of the active compound composition in a specific form (permanent memory shape) is placed and then the memory shape is fixed by inducing a chemical or physical change of the applied active ingredients; wherein, after a desired or undesired deformation of the shape memory, the original memory shape is recoverable by a physical stimulation substantially.
2. The method according to claim 1, characterized in that at least two active ingredients are contained in the active ingredient composition, which individually have no or only weak shape memory properties and confers a synergistically enhanced shape memory effect, when used together according to the method of claim 1 hairs.
AV lead according to claim 1, wherein - the first active ingredient is a crosslinkable macromer forming a shape memory polymer after cross-linking, wherein the macromer a) contains cross-linkable regions that by chemical - are crosslinkable bonds and b) thermoplastic regions that are not chemically cross-linkable are, - the memory is fixed in shape by chemical crosslinking of the macromer to form the shape memory polymer, and wherein the shape memory polymer at least one transition - which temperature Ttrans.
A method for hair treatment, wherein
- a by a process according to claim 3 programmed hairstyle (permanent shape) is heated to a temperature above T tran s,
- the hair is brought into a second (temporary) shape and
- the second shape is fixed by cooling to a temperature below T trans.
The method of claim 3 or 4, characterized in that the crosslinkable macromer is selected from compounds of the general formula Al (X) n -A2 wherein Al and A2 for reactive, chemically cross-linkable groups are available, and - (X) n- is a divalent , thermo-plastic polymer or oligomer is.
A method according to claim 5, characterized in that the crosslinkable macromer is selected from th substitutability having at least two acrylate or methacrylate polyesters, oligoesters, polyalkylene glycols, oligo alkylene glycols, polyalkylene carbonates and Oligoalkylencarbonaten.
7. The method according art` claim 6, characterized in that the crosslinkable macromer is selected dimethacrylate of poly (ε-caprolactone), poly dimethacrylate (DL-lactide), poly (L-lactide-co-glycolide) dimethacrylate, poly (ethylene glycol) dimethacrylate, poly (propylene glycol) dimethacrylate, PEG-block-PPG-PEG block-dimethacrylate, poly (ethylene adipate) dimethacrylate, Hexamethylencarbonatdimethacrylat.
8. The method according to any one of the preceding claims, characterized in that the composition additionally contains a macromer with only one terminal or pendant, chemically reactive group is contained.
9. The method of claim 1, wherein - the first active ingredient is a shape memory polymer, a) at least one crosslinkable by physical interaction hard segment having a first transition temperature T 'trans / which is above room temperature, and b) at least one soft segment which second with a transition temperature Ttrans 'which is below T' trans,, and - the memory shape is fixed by physical crosslinking of the shape memory polymers.
10. The method according to claim 9, characterized in that the shaping of the hair "occurs trans and that the subsequent fixing of the hair shape by cooling to a temperature below T 'under heating to a temperature of at least T trans is effected.
11. A method for hair treatment, wherein - a programmed by a method according to claim 9 or 10 hairstyle (permanent shape) is heated to a temperature between T 'trans and T tr a n s, - bringing the hair in a second (temporary) shape is and - the second shape is fixed by cooling to a temperature below T tr a n s.
12. A method for reprogramming a previously by a method according to Claim 9 programmed hairstyle (permanent shape) into a new permanent shape, wherein - the hair is heated to a temperature above T 'trans - is brought into a new form, and - then the new shape is fixed by cooling to a temperature below T'T r a n s.
13. The method according to any one of claims 9 to 12, characterized in that the shape memory polymer has a degree of crystallinity of 3 to 80% and that the ratio of the moduli of elasticity below and above T r is a ns at least twentieth
14. A method according to any one of claims 9 to 13, characterized in that the shape memory polymer is a copolyester-urethane.
15. The method according to claim 14, characterized in that the shape memory polymer is the reaction product of (a) two different macrodiols selected from α, polyesters CD-dihydroxy-, ω-dihydroxy-oligo esters, α, polylactones ω-dihydroxy and α, ω-dihydroxy-oligolactones and (b) at least one diisocyanate.
16. A process for recovery of a previously programmed by a method according to claim 1, 3, 9 or 12 hairstyle (permanent shape), wherein a hairstyle in a temporary shape according to claim 4 or claim 11 or a deformed by cold deformation of hair to a temperature above T tr ans is heated.
17. The method according to any one of the preceding claims, characterized in that the hydrophobic second active ingredient is selected from dimer diol, Dimerdiololigoethern, oligoester diols, dimer acid, PMS-divinyl ether, hydrophobic polymers, the hydrophobic surfactants with HLB values ​​<7, silicone compounds, organic oils, fats, waxes, glyceryl esters, Fettsäureestern, Fettalkoholestern.
18. The method according to claim 17, characterized in that the hydrophobic polymer is selected from polymers which contain at least one monomer, which is selected from Acrylsaurealkylestern Methacrylsäurealkylestem and wherein the alkyl groups have at least 6 carbon atoms.
19. The method according to claim 17, characterized in that the silicone compounds are selected from dimethylpolysiloxanes and dimethylsiloxane / alkylmethylsiloxane copolymers, wherein the alkyl groups have at least 6 carbon atoms.
20. The method according to any one of the preceding claims, characterized in that the drug composition comprises the first ingredient in an amount of 0.01 to 25.%, And the second active ingredient in an amount of 0.01 to 25 wt.% Contains.
21. The method according to any one of the preceding claims, characterized in that the active ingredient composition is present as a solution and water and at least one organic solvent.
22. The method according to claim 21, characterized in that the organic solvents are selected from ethanol, isopropanol, n-propanol and acetone.
23. A hair cosmetic composition comprising, in a suitable cosmetic base an active substance complex, said active substance complex comprises a first active substance (A) at least, which is chosen from materials which are alone or in combination with other substances in a position after application to to give hair and after carrying out a method according to one of claims 1 to 20 to the hair a shape memory effect, and (B) at least one second active ingredient which is selected from hydrophobic materials with a water solubility of <5 wt.% at 20 ° C.
24. The composition according to claim 23, characterized in that the first compound (A) is either a cross-linkable to a shape memory polymer macromer, wherein the crosslinked shape memory polymer ans and wherein the macromer a) contains at least one transition temperature T tr crosslinkable areas by chemical bonds can be crosslinked and b) thermoplastic regions that are not chemically cross-linked; and / or that the first active ingredient is a shape memory polymer comprising a) at least one crosslinkable by physical interaction hard segment having a first transition temperature 'trans? the above room temperature, and b) at least one soft segment with a second transition temperature T tran s / - which has is below T'T r a n s; and the second active ingredient (B) is selected from dimer diols, Dimerdiololigoethern, oligoester diols, dimer fatty acids, PMS-divinyl ether, hydrophobic polymers, the hydrophobic surfactants with HLB values ​​<7, silicone compounds, organic oils, fats and waxes; wherein the weight ratio of (A): (B) of 1: 1: 1 to 2.5.
25. The composition according to claim 24, characterized in that the hydrophobic polymer is selected from polymers which contain at least one monomer, which is selected from Acrylsaurealkylestern Methacrylsäurealkylestem and wherein the alkyl groups have at least 6 carbon atoms.
26. The composition of claim 24, characterized in that the silicone compounds are selected from dimethylpolysiloxanes and dimethylsiloxane / alkylmethylsiloxane copolymers, wherein the alkyl groups have at least 6 carbon atoms.
27. A composition according to any one of claims 23 to 26, characterized in that the shape memory polymer to 0.01 to 25 wt.% And the hydrophobic active ingredient in an amount of 0.01 to 25 wt.% Is included.
28. A composition according to any one of claims 23 to 27, characterized in that at least two active ingredients are contained, which individually have no or only weak shape memory properties and impart a synergistically increased shape memory effect, when used together according to the method of claim 1 hairs.
29. A cosmetic composition comprising a composition according to any one of claims 23 to 28, characterized in that it is in the form of a lotion, a spray lotion, a cream, a gel, a Gelschaums, an aerosol spray, a nonaerosol spray, aerosol foam, a non -Aerosolschaums is present, an O / W or W / O emulsion, a microemulsion or a hair wax.
30. Composition according to claim 29, characterized in that additionally 0.01 to 25 wt.% Are contained least one active ingredient selected from haircare substances, hair-setting agents and hair coloring agents.
EP20040741009 2003-07-30 2004-07-14 Method for producing shape memory effects in hair Withdrawn EP1648393A1 (en)

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DE2003134788 DE10334788A1 (en) 2003-07-30 2003-07-30 A process for the production of shape memory effects to hair in conjunction with hydrophobic active ingredients
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CN1829497A (en) 2006-09-06 application
US20080311050A1 (en) 2008-12-18 application
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DE10334788A1 (en) 2005-02-24 application
JP2007500142A (en) 2007-01-11 application

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