EP1682602A1

EP1682602A1 - Cosmetic compositions comprising polyol/polyester block polymers

Info

Publication number: EP1682602A1
Application number: EP04741008A
Authority: EP
Inventors: Tareq Ali Abdulla Hasson; Andreas Lendlein; Karl Kratz; Simone MÖRSHEIM; Yasmin Ghazlan; Susanne Birkel; Thomas Krause; Axel Kalbfleisch; Andrea Walter; Susanne Graner
Original assignee: MnemoScience GmbH
Current assignee: MnemoScience GmbH
Priority date: 2003-07-30
Filing date: 2004-07-14
Publication date: 2006-07-26
Also published as: WO2005012388A1; US20070009465A1; JP2007500141A; DE10334784A1; CN1849357A

Abstract

Disclosed is a cosmetic composition comprising a certain moiety of a block polymer that consists of at least one first block which represents a polyol selected among polyethers, dimerdiol, derivatives derived from dimerdiol, and polyesters from dicarboxylic acids with diols, and at least two additional blocks which represent polyesters of hydrocarboxylic acids or the lactones thereof.

Description

Cosmetic composition-i with polyol / polyester block polymers

The present invention relates to a cosmetic composition containing certain block polymers from polyol blocks and polyester blocks, and to methods for hair treatment using the block 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. These styling products facilitate e.g. as a gel the shape and

Creation of the hairstyle, improve the state of a created hairstyle as a hairspray and increase the volume of the hair as a setting foam. It is disadvantageous that the desired effects are only of relatively short duration and due to external influences such as combing, wind, high air humidity, contact with or on water

Sleep is quickly lost again. It is then usually necessary to create a new, time-consuming hairstyle and to reapply a styling preparation. 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. It is disadvantageous that the necessary chemical treatment of the hair with reducing and oxidizing agents cannot impair the hair structure. Another disadvantage of the previously known methods for hair reshaping is that it is not possible to undo a reshaping in a relatively simple manner, ie to move from one hairstyle shape to another without complex new creation. The object underlying the present invention was to provide a composition which, after a first hairstyle creation, enables simple, uncomplicated and quick restyling or restoration of the hairstyle, without the need to reapply the composition during restyling. Another object was to provide a method with which it is possible to achieve a restorable hair styling without damaging intervention in the hair structure, in particular a method which facilitates the re-creation of hairstyles after deformations of an originally created hairstyle due to external influences , The invention relates to a cosmetic composition comprising, in a suitable cosmetic base, at least one block polymer from at least one first block, which is a polyol selected from polyethers, oligoethers, hydrocarbons with a molecular weight of at least 400 g / mol and at least two alcoholic hydroxyl groups,

Oligoester diols and polyesters from dicarboxylic acids with diols and at least two further blocks, which are polyesters of hydroxycarboxylic acids or their lactones. A polyol in the sense of the invention is a compound which has at least two alcoholic hydroxyl groups. The hydrocarbons can be linear, branched, saturated, mono- or polyunsaturated. Poly- and oligoethers are polymeric or oligomeric compounds whose organic repeating units are held together by ether functionalities (COC). For the purposes of the invention, polyethers have at least 4 ether groups and at least 5 repeating units and oligoethers have one, two or three ether groups and 2 to 4 repeating units. Block ^polymers suitable according to the invention preferably consist of at least one hard segment and at least one soft segment and preferably have at least two transition temperatures ^{Ttrans uπ} -d T'trans, T'trans above room temperature (25 ° C.) and Ttrans below T'trans ,

The polymer segments are preferably oligomers or dihydroxy hydrocarbons, 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. The molecular weight of the block 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. They have a degree of crystallinity of preferably 3 to 80%, particularly preferably 3 to 60%. Both transition temperatures can be, for example, melting temperatures T _m or glass transition temperatures Tg. Above T trans, the polymer has a lower modulus of elasticity than below Ttrans- ^The ratio of the moduli of elasticity below and Ttrans above st preferably at least 10, more preferably at least 20. The lower transition temperature Ttrans i ^st preferably greater than room temperature (25 ° C) , in particular at least 30 ° C, particularly preferably at least 35 ° C or at least 40 ° C, and is the temperature above which the spontaneous regression of the permanent shape from the deformed or from the temporary shape occurs. Ttrans is preferably so far above the usual ambient temperatures that no significant, unintended, thermally induced deformation of the temporary hairstyle shape occurs at ambient temperature. Suitable ranges for Ttrans are, for example, from 25 to 100 ° C, from 30 to 75 ° C, from 35 to 70 ° C or from 40 to 60 ° C. The upper transition temperature T'trans ü ^e 3t above Ttrans and is the temperature above which the stamping of the permanent shape or the stamping of a permanent shape into a new permanent shape takes place and by falling below the permanent form is fixed. T'trans is preferably so far above Ttra s' that when the hairstyle is heated to a temperature above Ttrans 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. Preferably, T 'trans at least 10 ° C, more preferably at least 20 ° C or at least 30 ° C above Ttrans- The difference between T' trans ^nd Ttrans can, for example from 10 to 80 ° C, from 20 to 70 ° C, or 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 polymers P are e.g. those of the general formula A (B) n (I) where A is from an n-valent polyether or oligoether, hydrocarbons with a molecular weight of at least 400 g / mol and n alcoholic hydroxyl groups, oligoester diols or from a polyester of a dicarboxylic acid with a diol, is derived, B is a poly (hydroxycarboxylic acid) block and n is a number greater than or equal to two, preferably 2, 3 or 4. Preference is given to B-A-B triblock polymers, in particular block polymers with a single polyol block as the middle block, two terminal polyester blocks made from hydroxycarboxylic acids or their lactones and with terminal alcoholic hydroxy groups.

A preferably represents polyalkylene glycol ethers of polyhydric alcohols, pol (tetrahydrofuran), dimer diol, dimer diol oligoethers and oligoester diols (dihydroxy oligoester). The

Polyalkylene glycol ethers preferably have 2 to 6 carbon atoms per alkylene group, particularly preferred are poly (ethylene glycol) (PEG) and pol (propylene glycol) (PPG). Dimerdiol is the name for alpha, omega-C36 diols, which are obtained by dimerization of oleyl alcohol or can be prepared by hydrogenation of dimer fatty acids. Dimer fatty acid is a mixture of aliphatic, branched or cyclic C36 dicarboxylic acids (dimer acid), which can be prepared by dimerizing oleic acid or tall oil fatty acid (TOFA). Dimer diol can be obtained, for example, 908. under the trade designation Sovermol ^® Dimerdiololigoether are oligomers of dimer diol, produced by acid-catalyzed dehydration of dimer diol. Dimers, trimers and tetramers of dimer diol are preferred. Suitable commercial products are, for example, Sovermol ^® 909 with a molecular weight of approx. 1000 or Sovermol ^® 910 with a molecular weight of approx. 2000. Oligoester diols (dihydroxyolxgo esters) are reaction products of an oligomerization of a dicarboxylic acid with a diol, the reaction product having two hydroxyl groups - suitable dicarboxylic acids for example C3 to C20 dicarboxylic acids, preferably aliphatic C4 to C10 dicarboxylic acids. Aliphatic dicarboxylic acids are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid. Aromatic dicarboxylic acids are, for example, phthalic acid and terephthalic acid. Diol components of the oligoester diols are, for example, C2 to C30 diols, preferably aliphatic C5 to C20 diols. Also suitable are glycerol monoesters, in particular monoesters of glycerol with aliphatic C2 to C30 monocarboxylic acids, preferably C5 to C20 monocarboxylic acids.

The poly (hydroxycarboxylic acid) block B can be formed from hydroxycarboxylic acids, in particular monohydroxymonocarboxylic acids, which can have up to 30 carbon atoms and from their lactones or lactides. The poly (hydroxycarboxylic acid) block B can also be a

Copolymer of two or more different hydroxy carboxylic acids. Hydroxycarboxylic acids can be: saturated or unsaturated aliphatic hydroxycarboxylic acids, aromatic hydroxycarboxylic acids, alpha-hydroxycarboxylic acids, beta Hydroxycarboxylic acids, omega-hydroxycarboxylic acids, hydroxy fatty acids. Alpha-hydroxycarboxylic acids are, for example, glycolic acid, lactic acid or mandelic acid. Beta-hydroxycarboxylic acids are, for example, beta-hydroxyalkanoic acids such as beta-hydroxybutyric acid or beta-hydroxyvaleric acid. Hydroxy fatty acids are, for example, 12-hydroxystearic acid or ricinoleic acid. Aromatic hydroxyl acids are, for example, hydroxybenzoic acids, for example salicylic acid.

B preferably stands for poly (ε-caprolactone), polylactides, polyglycolides, poly (lactide-co-glycolide), poly (pentadecalactone), poly (caprolactone-co-lactide), poly (pentadecalactone-co-lactide), poly (pentadecalactone) -co-caprolactone). A particularly preferred polyester to be used according to the invention is a polyester based on lactide units or pentadecalactone units.

Preferred block copolymers are those of the general formula HO- [Bl-C (= 0) 0-] _n ι [YOJ _n2 [C (= 0) -B2-0-] _n3 H (Ia) Bl and B2 are the same or different and stand for branched, cyclic or linear alkylene groups with 1 to 40, preferably with 2 to 20 carbon atoms. Y stands for a branched, cyclic or linear alkylene group with 2 to 30 C atoms, preferably for ethylene and / or propylene groups, or for a block of dimer diol, dimer diol oligoether or oligoester diol, and where nl, n2 and n3 are the same or different numbers larger or are equal to zero, both n2 and the sum nl + n3 being greater than zero.

Polymers of the formula (Ia) are particularly preferred, where B1 and B2 are branched or linear alkylene groups having 2 to 20 carbon atoms, Y is an ethylene group and nl, n2 and n3 are greater than zero and are chosen such that the molecular weight of the Polymer is greater than or equal to 2000. Block copolymers with a polyethylene glycol middle block and end blocks made of polylactic acid or poly-ε-caprolactone are suitable, for example, the end blocks being terminated at the ends Hydroxy groups are substituted, the middle block has a molecular weight in the range from 500 to 20,000, preferably 2,000 to 10,000, and the average molecular weight of the block copolymer is from 2,000 to 50,000, preferably from 3,000 to 25,000.

The advantage of copolymers with a block structure is that the different properties and functions of the blocks can be combined in one polymer. The properties of the blocks, e.g. The hydrophilicity, the affinity for the hair or the transition temperatures can be adjusted independently of each other.

For the preparation of the block copolymers, for example, an oligomeric or polymeric diol can be used as a difunctional initiator for a ring-opening polymer ion (ROP). The initiator then represents the A block. Polyether diols, which are commercially available in various molecular weights, are preferably used as the initiator. PEO or PEG with a molecular weight of 4000 to 8000 g / mol is preferably used, particularly preferably with a molecular weight of 6000 and 8000 g / mol, which corresponds to the A block length. More preferred diols are dimer diol (Dimerfettdiol), commercially available under the trade name Sovermol ^® 908, having a molecular weight of 550 g / mol. The production of dimer diol is known. Dimerdiol can be prepared, for example, by hydrogenating dimeric oleic acid and / or its esters according to German patent DE-B 17 68 313. The general formula is HO-CH2-C34H66-CH2-OH. Dimerdiol oligoether, commercially available under the trade names Sovermol ^® 909, with a molecular weight of approx. 1000 g / mol, and Sovermol ^® 910, with a molecular weight of approx. 2000 g / mol. The general formula is HO-CH2-C3 H65-CH2- O- [CH -C34Hgg-CH2-0-] _n H where n is a number from 1 to 5, preferably 1, 2 or 3. Oligoester diols with molecular weights between 1000 and 6000 g / mol, which were synthesized from dicarboxylic acids and diols based on fat. The diols are based on fat. are in particular linear or branched aliphatic C2 to Ci4 diols, 12-hydroxystearyl alcohol, dimer fatty diol, dimer fatty diol oligoether with a molecular weight of 1000 to 2000, and glycerol monoesters with oleic acid, stearic acid or lauric acid. The dicarboxylic acids are preferably dimer fatty acid, adipic acid and azelaic acid.

The oligoester diols of the following general formulas are suitable: oligoester diols of dxmerdiol: H0-CH ₂ -C ₃ 4H ₆ 6-CH ₂ -0- [(0 =) CRC (= 0) -0-CH2-C ₃₄ H ₆ 6- CH2-0-] _n H oligoester diols of 12-hydroxystearyl alcohol:

HO- (CH ₂ ) H-CH (CGHI3> -O- C (0 =) CRC (= 0) -O- (CH ₂ ) ll-CH (C ₆ Hι ₃ ) -O-] _n H are particularly preferred Hydroxystearyl alcohol adipate diol and hydroxystearyl alcohol azeleate diol.Oligoester diols of glycerol monostearate:

H0-CH (CH ₂ -0-C (= 0) (C17H35)) -CH ₂ 0- [(0 =) CRC (= 0) -0-CH ₂ -CH- (CH ₂ 0- C (= 0 ) - (C ₁₇ H ₃₅ )) -CH2O-] _n H In all formulas, R stands for linear, aliphatic hydrocarbons with 4 to 36 C atoms and n for numbers greater than or equal to 1, preferably greater than or equal to 2.

The production of oligoester diols from diols and dicarboxylic acids is known in the prior art. They can be produced with or without the use of catalysts. All esterification catalysts such as sulfuric acid, phosphoric acid or p-toululsulfonic acid can be used as catalysts. Also tin compounds like tin diacctate, Tin oxide and tin oxalate resp. Titanium compounds such as B. Titanium (IV) isopropoxide can be used. P-Toluenesulfonic acid and titanium (IV) isopropoxide are preferred.

5 Cyclic esters or diesters can be used to introduce the B blocks, e.g. Dilactide, diglycolide, p-dioxanone, ε-caprolactone, ω-pentadecalactone or mixtures thereof. Dilactide, L, L-dilactide or ω -pentadecalactone is preferably used. The reaction is preferably carried out in bulk, optionally with the addition of a catalyst, such as. Dibutyltin (IV) oxide, dibutyltin (IV) di laurate, tin (II) dilaurate, tin (II) octanoate, titanium (IV) isopropoxide or lithium chloride. Dibutyltin (IV) oxide and tin (II) octanoate, in particular dibutyltin (IV) oxide, are preferred. If a catalyst is used, this can be done in amounts of 0.1 to 0.3 mol%. Since many of the possible catalysts, in particular the tin compounds, are toxic, the use of the triblock copolymers in materials for the cosmetic or medical field is necessary the remaining catalyst in the copolymer are removed. The respective 2.0 procedural conditions are known to the person skilled in the art and illustrated by the examples below -

The B block length can be variably adjusted via the molar ratio of monomer to initiator. The 25% by weight of A blocks in the block copolymers is preferably 40 to 90%.

Other suitable block copolymers are, for example, multiblock copolymers which can be obtained by reacting a diol 0 as initiator (block A) first with a first monomer (block B), then with a second monomer (block C).

Suitable block copolymers are, for example, star-shaped block copolymers, which are available if one instead of the diol Triol or tetrol is used as an initiator. The following are preferably used as trifunctional initiators: commercially available glycerol ethoxylate or glycerol propoxylate or glycerol propoxylate b-ethoxylate with a molecular weight of 200 to 6000 g / mol, particularly preferably with a molecular weight of 1000 and 3000 g / mol. The following are preferably used as tetrafunctional initiators: commercially available pentaerythritol ethoxylate or pentaerythritol propoxylate or pentaerythritol propoxylate ethoxylate with a molecular weight of 200 to 3000 g / mol, particularly preferably with a molecular weight of 500 and 2000 g / mol. In principle, diblock copolymers are also suitable -

The block polymers described are preferably end-capped with hydroxyl groups.

Compositions for hair treatment according to the invention contain at least one of the above-mentioned block polymers in an amount of preferably 0.01 to 25% by weight, particularly preferably 0.1 to 15% by weight in a suitable, preferably liquid, viscous or semi-solid medium. The composition can be in the form of a solution, dispersion, emulsion, suspension or latex. The liquid medium is preferably cosmetically acceptable and physiologically harmless.

The composition according to the invention is generally in the form of a solution or dispersion in a suitable solvent. Aqueous, alcoholic or aqueous-alcoholic solvents are particularly preferred. Suitable solvents are, for example, aliphatic C1 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. Solvents based on silicone are also suitable, in particular silicone oils based on linear or cyclic polydimethylsiloxanes (dimethicone or cyclomethicone). The solvents are preferably present in an amount of 0.5 to 99% by weight, particularly preferably in an amount of 40 to 90% by weight.

Compositions according to the invention can additionally contain 0.01 to 25% by weight of at least one hair-care, hair-setting 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 of synthetic or natural origin and have a nonionic, cationic, anionic or amphoteric character. Such a polymer additive, which can be contained in amounts of 0.01 to 25% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by weight, can also be a mixture of several

Polymer exist and are 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, or polyacrylamides, or polyacrylamides, or polyacrylamides, or polyacrylamides Polyethylene glycols with a molecular weight of 800 to 20,000 g / mol are used. Suitable synthetic, film-forming anionic polymers include crotonic acid / vinyl acetate copolymers and terpolymers made from acrylic acid, ethyl acrylate and Nt-butylacrylamide. Natural film-forming polymers or polymers produced therefrom by chemical conversion can also be used in the hair treatment composition according to the invention. Low molecular weight chitosan with a molecular weight of 30,000 to 70,000 g / mol or high molecular weight chitosan, organo-soluble derivatives of chitosan, mixtures of oligo-, mono- and disaccharides, Chinese balsam resin, cellulose derivatives such as hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol have proven successful , or shellac in neutralized or unneutralized form. Amphoteric polymers can also be used in the hair treatment composition according to the invention. Are suitable for. B-copolymers of octylacrylamide, t-butylaminoethyl methacrylate and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters. Among the cationic polymers which can be used according to the invention are copolymers of vinylpyrrolidone with guanated derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone / dimethylaminomethacrylate copied with diethyl sulfate. Other cationic polymers include the copolymer of

Vinylpyrrolidone with vinylimidazolium methochloride, the terpolymer made from dirnethyldiallylammonium chloride, sodium acrylate and acrylamide, the terpolymer made from vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcarprolactam, the guaternized ammonium salt made from hydroxyethyl cellulose and an epoxy substituted with trimethylammonu

Vinyl pyrrolidone / methacrylamidopropyl trimethyl ammonium chloride copolymer and diquaternary polydimethyl siloxanes. The consistency of the hair treatment agent 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 micro emulsion or a hair wax.

If the hair treatment composition according to the invention is in the form of an aerosol spray, it additionally contains 15 to 85% by weight, preferably 25 to 75% by weight, of a propellant and is filled in a pressure container with a spray head. Lower alkanes, such as e.g. n-butane, isobutane and propane, or their mixtures, as well as dimethyl ether or fluorohydrocarbons such as F 152a (1, 1-di luorethane) or F 134 (tetrafluoroethane) and furthermore, at the pressures under consideration, gaseous blowing agents such as 2, N2O and CO2 and mixtures of the above blowing agents are suitable.

If the hair treatment composition according to the invention is in the form of a sprayable non-aerosol hairspray, it is sprayed using 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. As a suitable mechanical spray device, 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 is continuously released as a result of the contraction of the elastic container when the spray valve is opened.

If the hair treatment composition according to the invention is in the form of a hair scent (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. A commercially available pump foamer or an aerosol foam head, for example, can be used as a suitable mechanical foaming device.

If the hair treatment composition according to the invention is in the form of a hair gel, it additionally contains at least one gel-forming substance in an amount of preferably 0.05 to 10, particularly preferably 0.1 to 2% by weight. The viscosity of the gel is preferably from 100 to 50,000 mm / s, particularly preferably from 1,000 to 15,000 mm / s at 25 ^α C, measured as a dynamic viscosity measurement with 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 additionally contains water-insoluble fat or wax substances or substances which give the composition a wax-like consistency in an amount of preferably 0.5 to 30% by weight. Suitable water-insoluble substances are, for example, emulsifiers with an HLB value below 7, silicone oils, silicone waxes, waxes (for example wax alcohols, wax acids, wax esters, and in particular natural waxes such as beeswax, carnauba wax, etc.), fatty alcohols, fatty acids, fatty acid esters or high molecular weight polyethylene glycols a molecular weight of 800 to 20,000, preferably from 2,000 to 10,000 g / mol. If the hair treatment composition according to the invention is in the form of a hair lotion, it is in the form of a substantially 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 front. Alcohols which can be used are, in particular, the lower C1 to C alcohols usually used for cosmetic purposes, such as, for example, ethanol and isopropanol.

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

In a preferred embodiment, the agent according to the invention is able to simultaneously enable both an improved hairstyle design and hair coloring. The agent is then formulated as a coloring hair treatment agent such as a color fixer, coloring cream, coloring foam, etc. It then contains at least one coloring substance. These can be organic dyes, in particular so-called direct dyes, or else inorganic pigments. The total amount of dyes in the agent according to the invention is about 0.01 to 7% by weight, preferably about 0.2 to 4% by weight. Direct dyes suitable for the agent according to the invention are, for example, triphenylmethane dyes, aromatic nitro dyes, azo dyes, quinone dyes, cationic or anionic dyes. Further dyes known and customary for hair dyeing, which may be present in the colorant according to the invention, can be found, inter alia, in E. Sagarin, "Cosmetics, Science and Technology", Interscience Publishers Inc., New York (1957), pages 503 ff. And H Janistyn, "Handbook of Cosmetics and Fragrances", Volume 3 (1973), pages 388 ff. And K. Schrader "Fundamentals and Recipes of Cosmetics", 2nd edition (1989), pages 782-815.

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

Pigments are preferably not nanopigments. The preferred particle size is 1 to 200 μm, in particular 3 to

150 μm, particularly preferably 10 to 100 μm. Inorganic pigments are preferred.

The hair treatment composition according to the invention preferably additionally contains at least one hair care substance in an amount of from 0.01 to 10, particularly preferably from 0.05 to 5% by weight. Preferred hair care substances are silicone compounds and cation-active substances which, owing to cationic or cationizable groups, in particular primary, secondary, tertiary or quaternary amine groups, have a substantivity to human hair. Suitable cationic substances are selected from cationic surfactants, betaine, a photere tensides, cationic polymers, silicone compounds with cationic or cationizable groups, cationically derivatized proteins or protein hydrolyzates and betaine.

Suitable silicone compounds are e.g. Polydimethylsiloxane (INCI: dimethicone), α-hydro-ω-hydroxypolyoxydimethylsilylene (INCI: dimethiconol), cyclic dimethylpolysiloxane (INCI.- cyclomethicone), trimethyl (octadecyloxy) silane (INCI: stearoxy trimethylsilane), dimethylsiloxane Copolyol), dimethylsiloxane / aminoalkylsiloxane copolymer with hydroxy end groups (INCI: amodimethicone), monomethylpolysiloxane with lauryl side chains and polyoxyethylene and / or polyoxypropylene end chains, (INCI: laurylmethicone copolyol), dimethylsiloxane / glycol copolymer acetate (INCI: acylethyl siloxane copolymers) (INCI: trimethylsilylamodimethicone).

Preferred silicone polymers are Dimethicone, Cyclomethicone and Dimethiconole. Mixtures of silicone polymers are also suitable, e.g. a mixture of dimethicone and dimethiconol. The names given in brackets above correspond to the INCI nomenclature (International Cosmetic Ingredients) as they are intended for the labeling of cosmetic active ingredients and auxiliary substances.

Usually, other known cosmetic additives can be added to the hair treatment composition according to the invention, for example non-setting, nonionic polymers such as polyethylene glycols, never setting, anionic and natural polymers and mixtures thereof in an amount of preferably 0.01 to 50% by weight. Perfume oils in an amount of 0.01 to 5% by weight, opacifiers such as ethylene glycol distearate in an amount of 0.01 to 5% by weight, wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, ethoxylated Fatty alcohols, fatty acid alkanolamides such as the esters of hydrogenated castor oil fatty acids in an amount of 0.1 to 30% by weight, in addition Humectants, dyes, light stabilizers, antioxidants and preservatives in an amount of 0.01 to 10% by weight. Another object of the invention is a method for hair treatment, wherein a composition according to the invention described above is applied to the hair, before, simultaneously or subsequently, the hair is brought into a specific shape under the action of heat and then the shape is fixed by cooling.

The shaping of the hair is expediently carried out by heating to a temperature of at least T'trans ^and the hair shape is fixed by cooling to a temperature below T'trans. Room temperature usually means ambient temperature, preferably at least 20 ° C, in warmer climates preferably at least 25 ° C. The composition can be applied to the hair in various ways, for example directly by spraying or indirectly by first applying it to the hand or to a suitable aid such as a comb, brush etc. and then distributing it in or on the hair. The consistency of the composition can be, for example, that of a solution, dispersion, lotion, thickened lotion, gel, foam, a semi-solid mass, creamy or waxy.

Another object of the invention is a method for embossing a second hairstyle shape on a programmed, retrievable first hairstyle shape. Here, a hairstyle (permanent shape) programmed by the above-mentioned method is first heated to a temperature above Ttrans or between T'trans Ttrans. The hair is then brought into the desired second (temporary) shape and the second shape is fixed by cooling to a temperature below Ttrans. Another object of the invention is a method for restoring a first hairstyle (permanent shape) previously programmed by the above method. For this purpose, a hairstyle in a temporary shape or a hairstyle deformed by cold deformation is heated to a temperature above ^τ trans. The permanent form regresses spontaneously and automatically.

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

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. Restoration of a programmed hairstyle in the sense of the invention means that the programmed hairstyle shape after a deformation to a recognizable extent, preferably to at least 60%, particularly preferably to at least 80%, based on the shape that arises after a first relaxation cycle. The degree of restoration can be measured, for example, by measuring the length of a lock of hair or a

Strands of hair are done. 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 be, for example, by simply unhooking the curls under the influence of gravity, by combing or brushing the hair, by wind or moisture, by mechanical influences while sleeping or lying down etc.

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) convert back without external force by just heating or by another energetic stimulus. Deformation and reconversion are possible several times. The degree to which the original, permanent form is achieved in a first relaxation cycle, consisting of deformation and re-transformation, is generally somewhat lower 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 50% and in the subsequent relaxation cycles preferably at least 60%, particularly preferably at least 80%. But it can also be 90% and more. The degree of reconversion can be measured, as in the case of conventional curl retention measurements, by simply measuring the length of a treated lock of hair or by known, suitable tensile-stretching experiments.

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 form crystalline regions store together. 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. H . can be triggered by removing solvents.

Figure 1 shows schematically the method for hair treatment - a strand of hair is wound on a winding body and sprayed with a liquid composition according to the invention containing a block polymer. By heat treatment with a suitable energy source, e.g. the desired shape is fixed in a hairdryer. Finally, the winding body is removed.

Figure 2 shows the deformation of an originally created hairstyle and its restoration. The curl in the original (permanent) shape has the length 1Q. The curl in the deformed form has the length l. The curl in the restored form has the length 1 ₂ . The degree of recovery (recovery) is calculated according to: Recovery = (lχ - 1 ₂ ) / (l - lo) -

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). Assuming a smooth streak On which a curl shape is stamped as a permanent shape and on which a second, smooth shape is then stamped as a temporary shape, the shape 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 actuator R = 6 according to M = (f / F) * (r / R) * 100 The memory factor Ideally it should not be below 20, preferably at least 25 or at least 30, particularly preferably between 35 and 100.

The following examples are intended to explain the subject matter of the invention in more detail. EXAMPLES The triblock copolymers used in the following examples are produced using the particular diols forming the middle block as initiator and esterification with the respective polyesters forming the end blocks by means of conventional esterification reactions.

Preparation of an oligoester diol Dicarboxylic acid (1 mol) and diol (1.2 to 1.5 mol) are mixed at 100 ° C. with stirring. The esterification reaction was then started by adding p-toluenesulfonic acid (1-5% by weight, based on the total mass). After the reaction has ended, the temperature is cooled to 40 ° C. and methylene chloride is added to dissolve the reaction mass. The product is precipitated in methanol, washed with methanol and dried in a vacuum drying cabinet. The average molar masses are determined by means of GPC (calibration with polystyrene).

Examples 1 to 56 Approx. 2-3% compositions of the following block copolymers are produced in ethanol / water (50:50) or ethanol / water / acetone (45: 45.-10).

Examples 57 to 100 Approx. 2-3% compositions of the following block copolymers are produced in ethanol / water / acetone (25:25:50).

Examples: hair treatment with triblock copolymers

Ac = acetone, W = water, Et = ethanol

Hair protection and manufacture of permanent form:

A strand of hair moistened with water and a length of 20 cm is twisted onto a hair roller and the polymer solution is applied (20-30 mg polymer / g hair). The treated section is heated to 70 ° C. for 30 minutes. After cooling to room temperature (about 25 ° C), the hair curler is removed. The curly strand (embossed permanent shape) had a length of about 4.5 cm.

Production of the temporary shape and restoration of the permanent shape: To produce the temporary shape (e.g. smooth), the curly 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 re-create a temporary shape (e.g. smooth), the curly strand is heated again to 55 ° C, Stretched to their full length (20 cm) and cooled to room temperature.

Examples of hair cosmetics

Example. L: Aerosol hair dryer lotion

Propellant filled into an aerosol can. Example 2: Aerosol hair dryer lotion 3.3 g block polymer No. 1 3.5 g octylacrylamide / acrylic acid / butylaminoethyl methacrylate / methyl methacrylate / hydroxypropyl methacrylate ® copolymer (amphomer LV 71) 0.57 g aminomethyl propanol 95% 0.20 g Perfume 0.02 g Baysilon Ol PD 5 (phenyl trimethicone) 10.00 g water ad 100 g ethanol The active ingredient solution is filled into an aerosol can in a ratio of 45 55 with DME as propellant.

The drug solution is filled in a ratio of 65:35 with propane / butane (2.7 bar) as a propellant into an aerosol can.

The active ingredient solution was filled in a 45:55 ratio with DME as propellant into an aerosol can.

Example 5: Aerosol foam fixer

Example 8: Aerosol foam fixer

Example 9: Aerosol foam fixer

Example 11: Non-Aerosol Hair Dryer Lot 4.5 g Block Polymer No. 9 0.45 g Vinyl Acetate / Crotonic Acid / Polyethylene Oxide Copolymer The composition can be filled in a packaging with a pump spray device and used as a non-aerosol spray.

Example 12: Non-Aerosol Hair Dryer Lotion

The composition can be filled in a packaging with a pump spray device and used as a non-Aexosol spray.

Example 13: Non-Aerosol Hair Dryer Lotion

The composition can be filled in a packaging with a pump spray device and used as a non-aerosol spray.

Example 15: Non-Aerosol Hair Dryer Lotion

Example 16s Non-aerosol hair dryer lotion

Example 17: Spray setting agent

Example 18: Spray setting agent

0.25 g perfume 0.20 g cetyltrimethylammonium chloride ad 100 g water The composition can be filled in a packaging with a pump spray device and used as a non-aerosol spray.

Example 19: Spray gel 5.2 g block polymer No. 7 20 g ethanol 0.1 g aminomethylpropanol 95% 0.2 g PΞG-40 Hydrogenated Castor Oil 0.2 g perfume 1.5 g carbomer ad 100 g water The composition can be in a packaging filled with a pump spray device and used as a non-aerosol spray.

Example 20: Spray gel

Example 21: Pump foam fastener

Example 23: Pump foam fixer

Example 24: Pump foam fixer

The aforementioned harkosmetic agents can alternatively or additionally contain another of the block polymers Nos. 1 to 100.

The abbreviations used in the examples mean: PEG-4k, PEG-6k, PEG-8k: polyethylene glycol with a molecular weight of 4000, 6000 or 8000 PDL: pentadecalactone; Lactone of 15-hydroxypentadecanoic acid PPDL: poly (pentadecalactone), poly (15-hydroxypentadecanoic acid) P-LL-LA: poly (L-lactic acid) P-DL-LA: poly (DL-lactic acid) PCL: poly (ε-caprolactone)

P (CL-co-LA): poly (e-caprolactone-co-DL-lactic acid) PCL-b-PPDL: poly (e-caprolactone) -block-poly (pentadecalactone) PEG (4k) -DMA, PEG (8k ) -DMA, PEG (10k) -DMA: poly (ethylene glycol) -dimethacrylate PLGA (7k) -DMA: poly (L-lactide-co-glycolide) -dimethacrylate PCI (10k) -DMA: poly (ε-caprolactone) - dimethacrylate D-OEt 1000: dimer diol oligoether Mn = 1000 (Sovermol 909) D-OEt 2000: dimer diol oligoether Mn = 2000 (Sovermol 910) D-OEs 1000: oligoester diol M _n = 1000 from glycerol monostearate and azelaic acid D-OEs 2000: Oligoester diol M _n = 2000 from hydroxystearyl alcohol and adipic acid

D-OEs 3000: oligoester diol M _n = 3000 from hydroxystearyl alcohol and azelaic acid D-OEs 4000: oligoester diol M _n = 4000 from hydroxystearyl alcohol and azelaic acid D-OEs 5000: oligoester diol M _n = 5000 from hydroxystearyl alcohol and azelaic acid

Claims

Patent claims

1. Cosmetic composition containing in a suitable cosmetic base at least one block polymer of at least a first block, which is a polyol selected from polyethers, oligoethers, hydrocarbons with a molecular weight of at least 400 g / mol and at least two alcoholic hydroxy groups , oligoesterdiols and polyesters from dicarboxylic acids with diols and at least two other blocks, which are polyesters of hydroxycarboxylic acids or their lactones.

2. Composition according to claim 1, characterized in that the block polymer a) at least one hard segment with a first transition temperature T'trans / ^d i ^e above room temperature, and b) at least one soft segment with a second transition temperature Ttrans which is below of 'trans.

3. Composition according to one of the preceding claims, characterized in that the block polymer has the formula A(B) _n , where A is an n-valent poly- or oligoether, hydrocarbons with a molecular weight of at least 400 g / mol and n alcoholic hydroxy groups , oligoesterdiols or from a polyester of a dicarboxylic acid with a diol, B is a poly (hydroxycarboxylic acid) block and n is a number greater than or equal to two.

Composition according to claim 3, characterized in that A is selected from polyalkylene glycol ethers of polyhydric alcohols, poly (tetrahydrofuran), dimer diol, dimer diol oligoethers, oligoesterdiols, B is selected from poly (ε-caprolactone), poly (pentadecanolactone), polylactides, polyglycolides, poly (lactide-co-glycolide) and n is 2, 3 or 4.

5. Composition according to one of the preceding claims, characterized in that the block polymer has a single polyol block as a middle block, two terminal polyester blocks of hydroxycarboxylic acids or their lactones with terminal alcoholic hydroxy groups.

6. Composition according to claim 5, characterized in that the block polymer has the general formula HO- [Bl-C(=0)0-.nl [Y-0-] _n [C (=0) -B2-0-] _n3 H, where B1 and B2 are the same or different and represent branched, cyclic or linear alkylene groups with 1 to 40 carbon atoms, Y represents a branched, cyclic or linear alkylene group with 2 to 30 carbon atoms or a polyester block of dicarboxylic acid and diol and nl, n2 and n3 are the same or different numbers greater than zero.

7. Composition according to claim 6, characterized in that B1 and B2 represent branched, cyclic or linear alkylene groups with 2 to 20 carbon atoms and Y represents ethylene and / or propylene groups.

8. Composition according to claim 7, characterized in that B1 and B2 represent branched or linear alkylene groups with 2 to 20 carbon atoms, Y is an ethylene group and nl, n2 and n3 are selected such that the molecular weight of the block polymer is greater than or equal to 2000 is.

9. Composition according to one of the preceding claims, characterized in that the block polymer has a Has a degree of crystallinity of 3 to 80% and that the ratio of the elastic moduli below and above t ns is at least 20.

10. Composition according to one of the preceding claims, characterized in that the block polymer is contained in 0.01 to 25% by weight.

11. Composition according to one of the preceding claims, characterized in that it additionally contains 0.01 to 25% by weight of at least one additional active ingredient selected from hair-care substances, hair-setting substances and hair-coloring substances.

12. Cosmetic agent containing a composition according to one of claims 1 to 10, 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 , a 0/W or W/O emulsion, a microemulsion or a hair wax.

13. Use of block polymers consisting of at least a first block, which is a polyol, selected from polyethers, hydrocarbons with a molecular weight of at least 400 g / mol and at least two alcoholic hydroxy groups, dimerdiol, derivatives derived from dimerdiol and polyesters from dicarbons ures with diols and at least two other blocks, which are polyesters of hydroxycarboxylic acids or their lactones, for hair treatment.

1 . Method for hair treatment, wherein a composition according to one of claims 1 to 10 is applied to the hair, before, simultaneously or subsequently the hair is brought into a specific shape under the influence of heat and - then the shape is fixed by cooling.

15. The method according to claim 14, characterized in that the hair is shaped by heating to a temperature of at least T'trans and that the hair shape is subsequently fixed by cooling to a temperature below T'trans.

16. A method for hair treatment, wherein a first hairstyle (permanent form) created by a method according to claim 14 or 15 is heated to a temperature between T'trans and Ttrans, the hair is brought into a second (temporary) form and the second form is fixed by cooling to a temperature below Ttrans.

17. A method for restoring a hairstyle (permanent form) previously programmed by a method according to one of claims 14 to 15, wherein a hairstyle in a temporary form according to claim 15 or a hairstyle deformed by cold deformation is heated to a temperature above Ttrans.

18. A method for converting a hairstyle previously created by a method according to claim 14 or 15 into a new hairstyle shape, wherein - the hairstyle is heated to a temperature above T'trans - is brought into a new shape and - then the new shape by cooling is fixed at a temperature below T'trans.