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

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

 METHOD FOR THE PRODUCTION OF SHAPED MEMORY EFFECTS ON HAIR

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

When 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 styling products facilitate e.g. B. as a gel the shaping and creation of the hairstyle, as a hair spray improve the status of a created hairstyle and increase as

Firming foam the volume of the hair. The disadvantage is 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 are reductively split in the hair, the hair is brought into the new shape and fixed by oxidative formation of new disulfide bonds. The disadvantage is that with the necessary chemical treatment of the hair

Reducing and oxidizing agents an impairment of the hair structure cannot be avoided. Another disadvantage of the previously known methods for hair reshaping is that it is not possible to reshape it relatively easy to undo, that is, to go from one hairstyle shape to another without time-consuming recreating.

JP 04-41416 discloses hair cosmetics which contain certain linear polyurethanes with a glass transition temperature Tg of 40-90 ° C. The method for hair treatment described corresponds to a treatment with a typical thermoplastic. After applying the composition, the hairstyle shape is created above Tg and fixed by cooling below Tg. When heated again above Tg, the polymer softens and a new hairstyle can be created. A method for a retrievable, reversible hair styling is not described.

The object underlying the present invention was to provide compositions with improved effectiveness and performance with regard to a retrievable hair shaping with a high degree of restoration of a programmed hairstyle shape. Improved effectiveness or performance can, for example, improve adhesion to the hair, improved durability of the effect, higher degrees of restoration of a programmed hairstyle form, etc. his. 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 reshaping several times and to return to a previously created, programmed, permanent hairstyle shape with high accuracy. Another object was to provide a method which makes it possible to undo deformations of a hairstyle which can be attributed to external influences in a simple manner and with high accuracy and return to a previously created, programmed, permanent hairstyle shape.

The object is achieved by a method for hair treatment, where

- An active ingredient composition is applied to the hair, the active ingredient composition (A) containing at least a first active ingredient or first active ingredient complex, which are selected or formed from substances which, alone or in combination with other substances, are capable of being applied after application Hair and after performing the treatment described below to give the hair a shape memory effect, and (B) contains at least one second active ingredient which is selected from hydrophobic substances; before, at the same time or after the application of the active ingredient composition, the hair is brought into a specific shape (permanent memory form) and - subsequently the memory shape is fixed by inducing a chemical or physical change in the applied active ingredients; 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. Hydrophobic substances in the sense of the invention are substances with a water solubility of <5% by weight, preferably <2% by weight at 20 ° C. The weight ratio of (A): (B) can e.g. 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.

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

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

- The first active ingredient of the composition applied to the hair is a crosslinkable macromer, which forms a shape memory polymer after crosslinking, 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 T _trans .

Another object of the invention is a method for embossing a second hairstyle shape on a programmed, retrievable first hairstyle shape. Here is first programmed by the above method hairstyle (permanent shape) to a temperature above _T trans _ns heated. Then the hair is in the desired one brought second (temporary) shape and the second shape is fixed by cooling to a temperature below T _trans .

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

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 in any shape (permanent shape), into which they spontaneously and after being deformed or after being impressed with a second shape (temporary shape) without outside

Convert force by simply 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 due to the removal of defects, textures, etc. which are still present at the beginning. A particularly high degree of re-conversion becomes but then achieved in the subsequent relaxation cycles. The degree of reconversion in the first relaxation cycle is preferably at least 30%, particularly preferably at least 40% and in the subsequent relaxation cycles preferably at least 40%, particularly preferably at least 50%. But it can also be 75%, 90% or 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 tensile-stretching experiments. The shape memory effect of hair is the property that a certain hairstyle shape (permanent Memory form) after a deformation can be restored spontaneously and without external force by simply heating or by another energetic stimulus, i.e. preferably at least 30%, particularly preferably at least 40% in a first relaxation cycle and preferably at least in the subsequent relaxation cycles 40%, particularly preferably at least 50% or 75%.

Macromers or prepolymers which can be crosslinked to form memory polymers in the sense 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 starts 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 T _trans . This can be a melting temperature T _m or a glass transition temperature T _g . Above T _{trans that} indicates

Polymer has a lower modulus of elasticity than below T _trans - the ratio of the elastic modulus below 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), in particular at least 30 ° C, particularly preferably at least 40 ° C, and is the temperature above which the spontaneous regression of the permanent form from the deformed or from the temporary form occurs.

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 which has a certain shape due to cross-linked shape memory polymers fixed in a permanent shape. Restoring a programmed hairstyle in the sense of the invention means that after a deformation the programmed hairstyle regresses to preferably at least 40%, particularly preferably at least 50% or 60%, based on the shape that arises after a first relaxation cycle. The degree of restoration can take place, for example, by measuring the length of a lock of hair or a strand of hair.

Suitable macromers or prepolymers which are chemically crosslinkable to form memory polymers are macromonomers which can be polymerized or crosslinked by individual chemical bonds. The chemically crosslinked polymers are also referred to in WO 99/42147 as thermoset polymers. The macromers and thermoset polymers described in WO 99/42147 are suitable according to the invention and form part of this application. Soft, thermoplastic segments (switching segments) with a transition temperature T _r a _n s are cross-linked by chemical, preferably covalent bonds. Switching segments and network points are therefore required, the network points fixing the permanent shape and the switching segments the temporary shape. The shape memory effect is based on the change in elasticity when the T _trans - Das exceeds or falls below The ratio of the elastic moduli below and above Ttans is preferably at least 20. The greater this ratio, the more pronounced the shape memory effect. There are four types of thermoset polymers with shape memory properties: network polymers, penetrating networks, semi-penetrating 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 cross-linkable and the other non-cross-linkable and both components cannot be separated by physical methods.

In principle, all synthetic or natural oligomers and polymers with reactive end or side groups are suitable which are suitable for the cross-linked shape memory polymer

Transition temperature Ttrans ^{un <} 3- impart suitable elasticity modules above and below Ttrans and the end or side groups either during production or subsequently by derivatization in a reactive form are available that allow a crosslinking reaction with the above 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, e.g. Polyethylene or polypropylene glycol or their block copolymers, the polymers or oligomers mentioned being substituted at 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, as well as 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".

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 (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 poor biodegradable polymer segments are poly (methacrylic acid), poly (acrylic acid), polyamides, polyethylene, polypropylene, polystyrene, Polyvinyl chloride, polyvinyl phenol and their mixtures and copolymers.

In a particularly preferred embodiment, the composition contains 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 are e.g. B. those of the general formula R- (X ') _n "A3 (II) where R is a monovalent organic radical, A3 is a reactive, chemically crosslinkable group and - (X') n- is a divalent, thermoplastic polymer or oligomer segment A3 is preferably an acrylate or methacrylate group The segment (X ') n preferably represents 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 carbon atoms mixtures of (AI) terminally esterified at both ends with acrylic or methacrylic acid polyalkylene glycols or polycaprolactones and (A2) terminally at one end with acrylic or methacrylic acid esterified polyalkylene glycol monoalkyl ethers, the alkylene groups preferably ethylene or propylene groups and the alkyl groups preferably C1 to C30 alkyl groups as component (AI), which can also be used alone ar is 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-block-PEG-dimethacrylate, poly (ethylene adipate) dimethacrylate, hexamethylene carbonate dimethacrylate. As component (B) are eg suitable: poly (ethylene glycol) monoacrylate,

Pol (propylene glycol) monoacrylate and their monoalkyl ether.

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

- The first active ingredient of the composition applied to the hair is a shape memory polymer which has at least two transition temperatures Tt _rans and T ' _trans and a) at least one hard segment which can be crosslinked by physical interaction and has a first transition temperature T'trans / - which is above room temperature, preferably more than 10 ° C above room temperature, and b) at least one soft segment with a second transition temperature Ttrans, which is below T ' _trans, preferably at least 10 ° C below T' _trans , - before, at the same time or after that Hair is brought into a certain (permanent) shape and - then the shape is fixed by physical crosslinking of the shape memory polymers.

The hair is expediently shaped by heating to a temperature of at least T ' _trans and the hair shape is fixed by cooling to a temperature below' _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 by spraying or indirectly by first applying it to the hand or to a suitable auxiliary such as. B. comb, brush, etc. and subsequent distribution in or on the hair. The consistency of the composition can, for example, be one Solution, dispersion, lotion, thickened lotion, gel, foam, a semi-solid mass, creamy or waxy.

Another object of the invention is a method for embossing on a second hairstyle shape on a programmed, retrievable first hairstyle shape. In this case, a programmed by the above method hairstyle (permanent shape) is first heated to a temperature between T 'and T _{trans tran} s heated. The hair is then brought into the desired second (temporary) shape and the second shape is fixed by cooling to a temperature below T _tas .

Another object of the invention is a method for restoring a first hairstyle (permanent

Shape) . For this purpose, a hairstyle in a temporary shape or a hairstyle deformed by cold deformation is heated to a temperature above T _trans . The permanent form regresses spontaneously and automatically. Cold shaping of a hairstyle means a hairstyle change at ambient temperature without the addition of additional heat by a hair dryer or similar devices. The deformation can be caused mechanically, for example by simply hanging 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 a different, new permanent shape. For this purpose, the original hairstyle is heated to a temperature above T ' _tran s and the hair in brought a new shape. Then the new shape is fixed by cooling to a temperature below T ' _trans .

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

According to the invention suitable physically crosslinkable shape memory polymers contain at least two transition temperatures T s and _ran T'ta _n s. Both transition temperatures can be, for example, melting temperatures T _m or glass transition temperatures T _g . The polymer has a lower modulus of elasticity above T _trans than below Ttrans. The ratio of the moduli of elasticity below and above Tt _r a _n s is preferably at least 10, particularly preferably at least 20. The lower transition temperature T _tr a _n s is preferred 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. T _trans is preferably so far above the usual ambient temperatures that there is no significant, unintended, thermally induced deformation of the temporary hairstyle shape at ambient temperature. Suitable ranges for T _tran s 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 lies above Tt _r a _ns and is the temperature above which the permanent shape is embossed or the permanent shape is converted into a new permanent shape and below which the permanent shape is fixed. T ' _trans is preferably so far above T _transr that when the hairstyle is heated to a temperature above T _rans to restore the permanent hairstyle _shape or to recreate a temporary hairstyle _shape while maintaining the permanent hairstyle shape, no significant, unintentional, thermally induced deformation of the permanent hairstyle shape occurs.

T't _r a _n s is preferably at least 10 ° C., particularly preferably at least 20 ° C. or at least 30 ° C. above Tras. The difference between T'trans and T _tr ans 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 crosslinks and has a transition temperature T ' _{t ans} which is above room temperature, preferably more than 10 ° C. above 20 ° C. The soft segment has a transition temperature T _tr ans / which is below T't _ran s, is 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 1,000 to 20,000 or 1,500 to 15,000. It can be linear di, tri, tetra or multiblock copolymers, branched, dendritic or grafted copolymers. They are preferably not linear polyether urethanes which contain bis (2-hydroxyethyl) hydroquinone. The molecular weight of the polymers can be, for example, from 30,000 to 1,000,000, preferably from 50,000 to 700,000 or from 70,000 to 400,000. Suitable physically cross-linked shape memory polymers are described in WO 99/42147 and are referred to there as thermoplastic polymers. The thermoplastic polymers described in WO 99/42147 and the production methods described there are suitable according to the invention and form part of this application. They have a degree of crystallinity of preferably 3 to 80%, particularly preferably 3 to 60%. The ratio of the elastic modulus above and below T _trans is preferably at least 10, particularly preferably at least 20. The polymer segments can be natural polymers such as. B. Proteins or polysaccharides 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 block and at least one different second type of block, the blocks causing the multiblock copolymer to have two different transition temperatures. Suitable multiblock copolymers are, in particular, those which are made 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 with further substituents. The alkylene group can be linear, branched or cyclic and preferably has 1 to 30 C atoms, particularly preferably 2 to 20 or 5 to 15 C atoms.

Particularly preferred shape memory polymers are the copolyester urethanes described in WO 99/42147, in particular the reaction products from (a) two different macrodiols, selected from α, ω-dihydroxy-polyesters, α, ω-dihydroxy-oligoesters,, ω-dihydroxy-polylactones and α, ω-dihydroxy-oligolactones and (b) at least one diisocyanate, preferably trimethylhexane-1,6-diisocyanate. Macrodiols made from poly (para-dioxanone) (PDX), poly (pentadecalactone) (PDL), poly (ε-caprolactone) (PCL), poly (L-lactide-co-glycolide) (PLGA) are particularly preferred. 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.

Hydrophobic agents Suitable hydrophobic active ingredients are, for example, oils, fats, waxes, fatty alcohols, fatty acids, hydrophobic polymers, hydrophobic surfactants, hydrophobic silicone compounds etc. Suitable hydrophobic surfactants are in particular those with 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, e.g. 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-3. Suitable oils are e.g. those with a melting point below 25 ° C and a boiling point preferably above

250 ° C, especially above 300 ° C. Vegetable or animal oils, mineral oils (Paraffinum liquidum), oily fatty acid esters or fatty alcohol esters are suitable. Hydrocarbon oils, e.g. Paraffin or isoparaffin oils, squalane, oils from fatty acids and polyols, especially triglycerides. Suitable vegetable oils are e.g. Sunflower oil, coconut oil, castor oil, lanolin oil, jojoba oil, corn oil, soybean oil. Suitable waxes are e.g. animal, vegetable, mineral and synthetic waxes, microcrystalline waxes, macrocrystalline waxes, solid paraffins, ozokerite, montan waxes, Fischer-Tropsch waxes,

Polyolefin waxes e.g. Polybutene, beeswax, wool wax and its derivatives such as Wool wax alcohols, candelilla wax, carnauba wax, Japanese wax, hardened fats, fatty acid esters and fatty acid glycerides, each with a solidification point above 40 ° C, wax alcohols, wax acids and polyethylene waxes etc. The waxes or wax-like substances have a solidification point above 40 ° C, preferably above 55 ° C. Suitable hydrophobic soft wax-like substances are e.g. Vaseline or semi-solid paraffins, e.g. Petrolatum (semi-solid mixture of hydrocarbons obtained from petroleum). The

Solidification points are usually in the range of approx. 25 ° C to 40 ° C. Hydrophobic polymers are preferably selected from polymers which contain at least one type of monomer which is selected from acrylic acid alkyl esters and methacrylic acid alkyl esters, the alkyl groups having at least 6 C atoms, preferably 8 to 30 C atoms.

Hydrophobic silicone compounds are preferably selected from silicone oils, silicone waxes, dimethylpolysiloxanes and dimethylsiloxane / alkylmethylsiloxane copolymers, the alkyl groups having 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 with alkyl side chains, the alkyl groups having 2 to 30, preferably at least 8, carbon atoms, particularly preferably 10 to 20 carbon atoms (for example stearyl dimethicone) , -Hydro-ω- hydroxypolyoxydimethylsilylene (dimethiconol), cyclic dimethylpolysiloxane (cyclomethicone), trimethyl (octadecyloxy) silane (stearoxytrimethylsilane), dimethylsiloxane / glycol copolymer (dimethicone copolyol), dimethylsiloxane / copolymer with aminomethylodoxy siloxane / aminomethylodoxyloxy siloxane / aminomethylodoxyloxy siloxane / aminoethyl siloxane polyoxysiloxane - And / or polyoxypropylene end chains, (laurylmethicone copolyol), dimethylsiloxane / glycol copolymer acetate (dimethicone copolyol acetate), dimethylsiloxane / aminoalkylsiloxane copolymer with trimethylsilyl end groups (trimethylsilylamodimethicone). Preferred silicone polymers are dimethicone, cyclomethicone and dimethiconone. Mixtures of silicone polymers are also suitable, such as a mixture of dimethicone and dimethiconol. The names given in brackets above correspond to the INCI nomenclature (International Cosmetic Ingredients) as they are intended for the labeling of cosmetic active ingredients and auxiliary substances. Particularly preferred hydrophobic substances are dimer acids and their derivatives. Dimer acids are dimerized fatty acids, especially the dimers of monounsaturated C8 to C30 fatty acids, eg oleic acid or tall oil acid (TOFA). Derivatives are, for example, dimer diol, dimer diol oligoether and oligoester diol. Dimer diol is the name for ω-C36 diols which can be prepared by dimerizing oleyl alcohol or by hydrogenating dimer fatty acids or their esters. Oligoester diols can be prepared from dimer diol by acid catalyzed dehydration. Oligoester diols are the dihydroxy esters made from dicarboxylic acids and diols based on fat. The molecular weight of the dimer diol oligoethers and the oligoester diols is preferably approximately 1000 to 10000, particularly preferably approximately 2000 to approximately 5000. Preferred oligomers are in particular dimers, trimers and tetramers. Preferred, commercially available diols are dimer diols (Sovermol ^® 908, Cognis, molecular weight approx. 550 g / mol) and dimer diol oligoether (Sovermol ^® 909, molecular weight approx. 1000 g / mol and Sovermol ^® 910, molecular weight approx. 2000 g / mol).

The hydrophobic ingredients can be low-volatility or high-volatility substances, with low-curvature substances remaining on the hair being preferred, in particular those with an evaporation number of preferably greater than 20, particularly preferably greater than 100. The evaporation number is defined as that Quotient of the evaporation time of the liquid to be tested and the evaporation time of diethyl ether as comparison liquid. In a preferred embodiment, the hair treatment composition according to the invention contains both at least one non-volatile hydrophobic substance and at least one highly volatile hydrophobic substance with an evaporation number of less than 20.

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

The composition according to the invention is generally in the form of a solution or dispersion in a suitable solution or. Dispersant before. Water, organic solvents and mixtures of water and are particularly preferred. at least one organic solvent. Preferred organic solvents are e.g. Alcohols and acetone. Suitable solvents are e.g. aliphatic linear or branched Cl to C4 alcohols or a mixture of water with one of these alcohols. However, other organic solvents can also be used, in particular unbranched or branched

Hydrocarbons such as pentane, hexane, isopentane, cyclic hydrocarbons such as cyclopentane and cyclohexane, organic linear or cyclic ethers, for example tetrahydrofuran (THF) or liquid organic esters, for example ethyl acetate, may be mentioned. Solvents based on silicone are also suitable, in particular silicone oils based on linear or cyclic polydimethylsiloxanes (dimethicone or cyclomethicone). volatile silicones with boiling points below 200 ° C. are preferred. Other solvents are acetone, tetrahydrofuran, chloroform etc. The solvents are preferably in an amount of 0.5 to 99% by weight, particularly preferably in an amount of from 10 to 97% by weight, from 20 to 95% by weight or from 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 agents are in particular the known, conventional film-forming and hair-fixing polymers. The film-forming and hair-fixing polymer can be synthetic or natural in nature and non-ionic, cationic, anionic or amphoteric in character. Such a polymer additive, which can be contained in amounts of 0.01 to 25 wt.%, Preferably 0.1 to 20 wt.%, Particularly preferably from 0.5 to 15 wt.%, Can also consist of a mixture of several polymers exist and be modified by the addition of other polymers with thickening effect in its hair-setting properties. According to the invention, film-forming, hair-fixing polymers are understood to be 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 vinyl pyrrolidone, homopolymers of N-vinylformamide, copolymers of vinyl pyrrolidone and vinyl acetate, terpolymers of vinyl pyrrolidone, vinyl acetate and vinyl propionate,

Polyacrylamides, polyvinyl alcohols, or polyethylene glycols with a molecular weight of 800 to 20,000 g / mol can be used. Suitable synthetic, film-forming anionic polymers should be mentioned 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, for example Chinese balsam resin, cellulose derivatives such as hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol, or shellac in neutralized or unneutralized form. Amphoteric polymers can also be used in the invention

Hair treatment agents are used. Are suitable for. B. copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters.

The consistency of the hair treatment composition according to the invention can be increased by adding thickeners. Homopolymers of acrylic acid with a molecular weight of 2,000,000 to 6,000,000 g / mol are suitable for this purpose, for example. 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.

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

If the hair treatment composition according to the invention is in the form of an aerosol spray, it additionally contains 15 to 85% by weight, preferably 25 to 75% by weight of a blowing agent and is filled in a pressure vessel with a spray head. Lower alkanes, such as n-butane, isobutane and propane, or also their mixtures, and also dimethyl ether or fluorocarbons such as F 152a (1,1-difluoroethane) or F 134 (tetrafluoroethane) and, furthermore, gaseous form as blowing agents are also present as blowing agents Blowing agents such as N2, N2O and CO2 and mixtures of the above-mentioned blowing agents are suitable.

If the hair treatment composition according to the invention is in the form of a sprayable non-erosol hairspray, it is sprayed with the aid of a suitable mechanically operated spraying device. Mechanical spraying devices are to be understood as devices which make it possible to spray a composition without using a propellant. A suitable mechanical spray device can be, for example, a spray pump or an elastic container provided with a spray valve, in which the cosmetic agent according to the invention is filled under pressure, the elastic container expanding and from which the agent continuously as a result of the contraction of the elastic container when the spray valve is opened is used.

If the hair treatment composition according to the invention is in the form of a hair foam (mousse), it contains at least one customary foaming substance known for this. 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, as an additional component, a device for foaming the composition. 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. As a suitable mechanical foaming device For example, a commercially available pump foam or an aerosol foam head can be used.

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

If the hair treatment composition according to the invention is in the form of a hair wax, it contains water-insoluble fat or wax substances or substances in an amount which give the composition a wax-like consistency, 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.

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

Hair lotion is present, it is present as an essentially non-viscous or slightly viscous, flowable solution, dispersion or emulsion with a content of at least 10% by weight, preferably 20 to 95% by weight, of a cosmetically acceptable alcohol. In particular, the lower C1 to C4 alcohols usually used for cosmetic purposes, such as ethanol and isopropanol, can be used as alcohols. If the hair treatment composition according to the invention is in the form of a hair cream, it is preferably in the form of an emulsion and either additionally contains viscosity-imparting ingredients in an amount of 0.1 to 10% by weight or the required viscosity and creamy consistency is achieved by micelle formation with the aid of suitable emulsifiers , Fatty acids, fatty alcohols, waxing etc.; c. built up in the usual way.

In a preferred embodiment, the agent according to the invention is capable of simultaneously embossing a retrievable hairstyle as well as hair coloring. The agent is then as a coloring hair treatment agent such. B. as a color fixer, coloring cream, coloring foam etc. formulated. It then contains at least one coloring substance. These can be organic dyes, in particular so-called direct dyes, or else inorganic pigments. The total amount of dyes in the composition according to the invention is approximately 0.01 to 7% by weight, preferably approximately 0.2 to 4% by weight. Direct dyes suitable for the agent according to the invention are, for example, triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinone dyes, cationic or anionic dyes.

Suitable hair-coloring pigments are colorants which are practically insoluble in the application medium and can be inorganic or organic. Inorganic-organic mixed pigments are also possible. The pigments are preferably not nano-pigments. The preferred particle size is 1 to 200 μm, in particular 3 to 150 μm, particularly preferably 10 to 100 μm. Inorganic pigments are preferred. The hair treatment composition according to the invention preferably additionally contains at least one hair care substance in an amount of 0.01 to 10, particularly preferably 0.05 to 5,% by weight. %. Preferred hair-care substances are cation-active substances. Cationic substances are characterized by the fact that they either carry at least one permanently cationic group in the molecule, e.g. B. an iminium group or an ammonium group, in particular a quaternary ammonium group, or that they carry at least one group which is cationizable, e.g. a primary, secondary or tertiary amine group which can be cationized by protonation, with quaternary ammonium groups being preferred. The cationic active ingredient is a substance which, due to the cationic or cationizable group, has a substantivity to human hair. Suitable cationic substances are e.g. B. Surfactants with cationic or cationizable groups, in particular cationic surfactants, betaine or amphoteric surfactants; Polymers with cationic or cationizable groups, in particular cationic, betaine or amphoteric polymers; Silicone compounds with cationic or cationizable groups, in particular diquaternary or polyquaternary siloxanes or amodimethicones; cationically derivatized proteins; cationically derivatized protein hydrolyzates or betaine.

Usually, other known cosmetic additives can be added to the hair treatment composition according to the invention, eg. B. non-setting, non-ionic 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. %. Also perfume oils and fragrances in an amount of 0.01 to 5% by weight. %,

Opacifiers such as ethylene glycol distearate in an amount of 0.01 to 5 wt. %, Wetting agents or emulsifiers, in particular anionic or nonionic surfactants such as fatty alcohol sulfates, ethoxylated fatty alcohols, Fatty acid alkanolamides such as the esters 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.

FIG. 1 schematically shows a possible method for producing a permanent hairstyle shape that can be called up. A lock of hair is wound on a winding body and sprayed with a solution according to the invention containing a crosslinkable macromer. The desired permanent shape is fixed by irradiation with a suitable energy source, for example a UV lamp. Finally, the winding body is removed. Figure 2 shows the deformation of a permanent hairstyle shape and restoration of the permanent shape from the temporary shape. The curl in the permanent form has the length lo - The curl in the deformed form has the length li. The curl in the restored form has the length I2 • The degree of recovery (recovery) is calculated according to: Recovery = di - 12 ⁾ / di - io ⁾ .

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 (shape factor) and the resetting of the permanent shape from the temporary shape (reset factor, degree of restoration). If a smooth streak is assumed, on which a curl shape is impressed as a permanent shape and then a second, smooth shape is impressed as a temporary shape, 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 form factor f, the maximum form factor F = 4, the respective reset factor r and the maximum reset factor R = 6 according to M = (f / F) * (r / R) * 100 The memory factor should ideally not less than 25, preferably between 25 and 33.3, particularly preferably between 37 and 100. The following examples are intended to explain the subject matter of the invention in more detail.

Examples

Examples 1-12 Compositions are prepared in accordance with Table 1 (quantities in g). Table 1

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

a product from Aldrich 10) Castoryl Maleate, a product from ISP 'Stearyl Dimethicone, a product from Clariant

The memory factor M is determined using the method described above.

To produce the permanent shape, a strand of water, 20 cm long, moistened with water is twisted onto a hair roller and the polymer solution is applied (20-30 mg polymer / g hair). The treated strand is fixed for 30 minutes at 70 ° C under UV light. After cooling to about 25 ° C, the hair roller is removed. The curly strand (embossed permanent shape) had a length of about 4.5 cm. To create the temporary shape (e.g. smooth), the wavy strand is heated to approx. 55 ° C, stretched to its original, full length (20 cm) and cooled to room temperature. To restore the permanent shape, the smooth strand is heated to approx. 55 ° C. At this temperature, the streak contracted spontaneously into a permanent shape (curled). To restore the permanent shape (e.g. smooth), the wavy strand is heated again to 55 ° C, stretched to its full length (20 cm) and cooled to room temperature.

Examples with crosslinkable macromers The following macromers which can be crosslinked to form memory polymers are used in the hair treatment compositions below. The macromers are prepared analogously to that described in WO 99/42147. Ml PEG (4k) -DMA, polyethylene glycol with a molecular weight of approx. 4000, twice esterified with methacrylic acid M2 PEG (8k) -DMA, polyethylene glycol with a molecular weight of approx. 8000, twice esterified with methacrylic acid M3 PEG (lOk) -DMA, polyethylene glycol with a molecular weight of approx. 10000, twice esterified with methacrylic acid M4 PLGA (7k) -DMA, poly (L-lactide-cσ-glycolide) -dimethacrylate with a molecular weight of approx. 7000 M5 PCI (10k ) -DMA, poly (ε-caprolactone) dimethacrylate with a molecular weight of approx. 10,000

The following hair treatment compositions were used as described in Example 1 with similar results.

Example 13: Non-Aerosol Spray Lotion 5.0 g Macromer Ml 0.5 g PVP / VA Copolymer 0.5 g Luviquat ^® FC 550 ³⁾ 0.5 g Tetraethoxylaurylether 1 g Dimethylpolysiloxane (Wacker-Belsil ^® DM 500) 0.5 g Polysorbate 40 Ad 100 g ethanol '40% solution of methyl vinyl imidazolium chloride / vinyl pyrrolidone copolymer (polyquaternium-IS) in water

The lotion is sprayed directly onto dry or damp hair using a commercially available spray pump.

Example 14: Liquid strengthener with memory effect 6.0 g macromer M2 5.0 g cyclo-octamethyltetrasiloxane 5.0 g vinyl pyrrolidone / vinyl acetate copolymer 2.0 g dihydroxy-polydimethylsiloxane, 12% in cyclodimethylsiloxane (Abil OSW 12 from Goldschmidt / Germany) ad 100 g pentane

Example 15: Hair wax with memory effect 7 g macromer M3 6 g ethanol 4 g cetyl alcohol 4 g petrolatum 3 g ceresin 3 g carnauba wax 2 g ceteareth-25 2 g polyvinylpyrrolidone 1.5 g mineral oil 1.5 g dicaprylyl maleate 0.5 g carbomer 0.4 g aminomethyl propanol ad 100 g water

Example 16 i Memory fluid hair fluid 3 g Macromer M4 0.6 g behenyltrimethylammonium chloride 0.5 g sunflower oil 0.5 g 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. Preservative, fragrance ad 100 g water

Example 17: Aerosol foam with memory effect 4 g Macromer M5 1 g Dow Corning DC 1401 Fluid (Dimethiconol / Cyclomethicone 13/87) 1 g glucose 0.6 g polyvinylpyrroidone 0.8 g Abil Quat ^® 3272 (Quaternium-80) 0.2 g cetyltrimethylammonium chloride 0.2 g polyquaternium-11 0.2 g silica 0.1 g Laureth-2 ad 100 g water The composition is mixed with 5% by weight of propane / butane filled in a pressure-resistant aerosol packaging with a foam head.

In Examples 14 to 17, the macromer used in each case can be exchanged in whole or in part for one of the other macromers Ml to M5 with similar results.

Examples with thermoplastic shape memory polymer

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

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

_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 water

Ad 100 g isopropanol

Example 19: Aerosol foam shape memory g 6 g of polymer P2 1 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 peel wax ad 100 g water

The composition is filled with 5% by weight propane / butane in a pressure-resistant aerosol packaging with a foam head.

Example 20: Liquid color fastener with memory 4.0 g polymer P7 2.0 g cyclo-octamethyltetrasiloxane 0.5 g 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 Basic Violet 14 (CI 42595) 0.01 g Basic Blue 7 (CI 42595) 20, 0 g pentane ad 100 g propanol

Example 21: Hairspray with memory effect 5.0 g polymer P8 0.5 g cyclo-octamethyltetrasiloxane 0.5 g dimethiconol (Silicone Fluid F 212 from Wacker / Germany) 5.0 g vinyl pyrrolidone / vinyl acetate copolymer 35 g propane / butane ad 100 g pentane

Example 22: Hair wax with memory effect 8 g polymer P3 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 cetyltrimethylammonium chloride 0.5 g polyvinylpyrrolidone / Vinyl acetate copolymer ad 100 g of water In Examples 18 to 22, the one used in each case

Partial or partial shape memory polymer against one of the other

Polymers P1 to P8 are exchanged with similar results.

Claims

claims

1. A method for hair treatment, wherein - an active ingredient composition is applied to the hair, the active ingredient composition (A) containing at least one first active ingredient or first active ingredient complex, which are selected or formed from substances which, alone or in combination with further substances, in are able to impart a shape memory effect to the hair after application to hair and after carrying out the treatment described below, and the active ingredient composition (B) contains at least one second active ingredient which is selected from hydrophobic substances with a water solubility of <5 % By weight at 20 ° C; 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; after an intentional or unwanted deformation of the shape of the memory, the original shape of the memory can essentially be restored by physical stimulation.

2. The method according to claim 1, characterized in that the active ingredient composition contains at least two active ingredients which individually have no or only weak shape memory properties and which, when used together according to the method of claim 1, give hair a synergistically increased shape memory effect.

The method according to claim 1, wherein - the first active ingredient is a crosslinkable macromer which forms a shape memory polymer after crosslinking, the macromer containing a) crosslinkable regions which can be crosslinked by chemical bonds and b) thermoplastic regions which are not chemically crosslinkable - The shape of the memory 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.

Process for hair treatment, wherein

a hairstyle (permanent shape) programmed by a method according to claim 3 is heated to a temperature above T _trans ,

- the hair is brought into a second (temporary) shape and

- The second form is fixed by cooling to a temperature below T _trans .

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

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

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

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

9. The method of claim 1, wherein - the first active ingredient is a shape memory polymer which a) at least one hard segment that can be crosslinked by physical interaction with a first transition temperature T'trans / which is above room temperature, and b) at least one soft segment with a second one Transition temperature Ttrans', which is below T'trans, and - the shape of the memory 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 takes place with heating to a temperature of at least T ' _trans and that Subsequent fixation of the hair shape is carried out by cooling to a temperature below T ' _trans .

11. A method for hair treatment, wherein - a hairstyle (permanent shape) programmed by a method according to claim 9 or 10 is heated to a temperature between T'trans and T _tr a _n s, - the hair is brought into a second (temporary) shape is and - the second form is fixed by cooling to a temperature below T _tr a _n s.

12. A method for reprogramming a hairstyle (permanent shape) previously programmed by a method according to claim 9 into a new permanent shape, wherein - the hairstyle is heated to a temperature above T ' _trans - is brought into a new shape and - then the new one Form 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 elastic modules below and above t _r a _{ns is} at least 20.

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

15. The method according to claim 14, characterized in that the shape memory polymer, the reaction product of (a) two different macrodiols selected from α, CD-dihydroxy polyesters,, ω-dihydroxy-oligoesters, α, ω-dihydroxy-polylactones and α, ω-dihydroxy-oligolactones and (b) at least one diisocyanate.

16. A method of restoring a hairstyle (permanent shape) previously programmed by a method according to claim 1, 3, 9 or 12, wherein a hairstyle in a temporary shape according to claim 4 or claim 11 or a hairstyle deformed by cold deformation 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, dimer diol oligoethers, oligoester diols, dimer acid, PMS divinyl ether, hydrophobic polymers, hydrophobic surfactants with HLB values <7, silicone compounds, organic oils, Fats, waxes, glyceryl esters, fatty acid esters, fatty alcohol esters.

18. The method according to claim 17, characterized in that the hydrophobic polymer is selected from polymers which contain at least one type of monomer which is selected from acrylic acid alkyl esters and methacrylic acid alkyl esters, the alkyl groups having 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, the alkyl groups having at least 6 carbon atoms.

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

21. The method according to any one of the preceding claims, characterized in that the active substance composition is in the form of a solution and contains 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. Hair cosmetic composition containing an active ingredient complex in a suitable cosmetic base, the active ingredient complex (A) containing at least one first active ingredient, which is selected from substances which, alone or in combination with other substances, are capable of being applied after application Hair and after performing a method according to any one of claims 1 to 20 to give the hair a shape memory effect, and (B) contains at least one second active ingredient which is selected from hydrophobic substances with a water solubility of <5 wt.% At 20 ° C.

24. The composition according to claim 23, characterized in that the first active ingredient (A) is either a macromer which can be crosslinked to form a shape memory polymer, the crosslinked shape memory polymer having at least one transition temperature T _tr ans and wherein the macromer a) contains crosslinkable regions which are chemically Bindings are networkable and b) contains thermoplastic areas that are not chemically crosslinkable; and / or that the first active ingredient is a shape memory polymer which a) has at least one hard segment which can be crosslinked by physical interaction and has a first transition temperature 'trans _? which is above room temperature, and b) has at least one soft segment with a second transition temperature T _tran s _/ - which is below T't _r a _n s; and the second active ingredient (B) is selected from dimer diols, dimer diol oligoethers, oligoester diols, dimer fatty acids, PMS divinyl ether, hydrophobic polymers, hydrophobic surfactants with HLB values <7, silicone compounds, organic oils, fats and waxes; wherein the weight ratio of (A): (B) is from 1: 1 to 2.5: 1.

25. The composition according to claim 24, characterized in that the hydrophobic polymer is selected from polymers which contain at least one type of monomer which is selected from acrylic acid alkyl esters and methacrylic acid alkyl esters, the alkyl groups having at least 6 carbon atoms.

26. The composition according to claim 24, characterized in that the silicone compounds are selected from dimethylpolysiloxanes and dimethylsiloxane / alkylmethylsiloxane copolymers, the alkyl groups having at least 6 carbon atoms.

27. The composition according to any one of claims 23 to 26, characterized in that the shape memory polymer is contained in an amount of 0.01 to 25% by weight and the hydrophobic active ingredient in an amount of 0.01 to 25% by weight.

28. The composition according to any one of claims 23 to 27, 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.

29. Cosmetic composition containing 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 gel foam, an aerosol spray, a non-aerosol spray, an aerosol foam, a non Aerosol foam, an O / W or W / O emulsion, a microemulsion or a hair wax.

30. Composition according to claim 29, 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.