Polymer combination for a shine-producing cosmetic hair treatment agent having strong hold and good hair feel

0001"Polymer combination for glossy cosmetic hair treatment agents with strong hold and good hair feel"

0002The present invention relates to agents for hair treatment containing at least one special anionic copolymer derived from vinylaromatic compounds in combination with at least one special anionic copolymer with silicone groups, the use of these agents for temporary shaping and / or for the care of keratin fibers and aerosol sprays or aerosol foams based this means.

0003In principle, keratin-containing fibers are understood to mean all animal hair, for example wool, horsehair, angora hair, furs, feathers and products or textiles made therefrom. However, the keratin fibers are preferably human hair.

0004An appealing looking hairstyle is now generally regarded as an indispensable part of a well-groomed exterior. Due to current fashion trends, hairstyles are always considered chic, which for many hair types can only be built up using setting agents or can be maintained for a longer period of time up to several days. Therefore, hair treatment agents that serve to permanently or temporarily shape the hair play an important role. Temporary shapes that are supposed to give a good hold without impairing the healthy appearance of the hair, such as, for example, its shine, can be achieved, for example, by hair sprays, hair waxes, hair gels, hair foams, blow dryer waves, etc.

0005Corresponding agents for temporary shaping usually contain synthetic polymers as the shaping component. Preparations which contain a dissolved or dispersed polymer can be applied to the hair by means of propellant gases or by a pump mechanism. However, hair gels and hair waxes in particular are generally not applied directly to the hair, but rather are distributed in the hair by means of a comb or the hands.

0006The most important property of an agent for temporarily deforming keratin fibers, hereinafter also referred to as styling agent, is to give the treated fibers as strong a hold as possible in the shape produced. If the keratin fibers are human hair, one also speaks of strong hairstyle hold or of the high degree of hold of the styling agent. The hairstyle hold is essentially determined by the type and amount of the synthetic polymer used, although there may also be an influence of the other components of the styling agent. In addition to a high degree of hold, styling agents have to meet a whole range of other requirements. These can be rough in properties on the hair, properties of the respective formulation, e.g. Properties of the foam, the gel or the sprayed aerosol, and properties relating to the handling of the styling agent can be subdivided, the properties on the hair being of particular importance. Particularly noteworthy are moisture resistance, low stickiness and a balanced conditioning effect. Furthermore, a styling agent should be universally applicable for all hair types if possible.

0007In order to meet the different requirements, a large number of synthetic polymers have already been developed that are used in styling agents. The polymers can be divided into cationic, anionic, nonionic and amphoteric film-forming and / or setting polymers. Ideally, the polymers form a polymer film when used on hair, which on the one hand gives the hairstyle a strong hold, but on the other hand is sufficiently flexible so that it does not break under stress. If the polymer film is too brittle, so-called film patches are formed, i.e. residues that come off when the hair moves and give the impression that the user of the corresponding styling agent has dandruff. In addition, the hair coated with a setting polymer often feels rough.

0008Furthermore, the temporarily styled hair should look healthy and natural in addition to the strong hairstyle hold. The hair shine plays an outstanding role in this. Therefore, so-called brighteners are often added to the hair styling agents in sufficient quantities. These brighteners are, for example, oils or gloss-giving pigments such as mica particles. Shining particles have the disadvantage that they separate from the hair over time and, for example, after a while on clothing or facial skin. Oils weigh down the hair and sometimes lead to poorer adhesion of the film-forming or setting polymers to the hair. This may lead to the disadvantage that the embossed hairstyle cannot be fixed for a sufficient period of time by the film-forming or setting polymers. The hairstyle detaches faster.

0009It was therefore an object of the present invention to provide a means for temporarily deforming and / or caring for keratin fibers, which is distinguished by a high degree of hold, an excellent gloss on the keratin-containing fibers and good sensor technology of the keratin-containing fibers (especially a soft feeling of hair).

0010It has now surprisingly been found that this can be achieved by combining a special fixing anionic copolymer with a further special crosslinked anionic copolymer. A first subject of the present invention is therefore an agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0011at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (II) and at least one structural unit of the formula III

0012<img file="WO2011069786A2_D0001.tif" />

0013wherein

0014R represents a hydrogen atom or a methyl group,

0015represents a hydrogen atom or a methyl group

0016R³ stands for a (Ci to C₂o) alkyl group, a (C₂ to C₆) Hydroxyalkyl group or a group ^*- (CH₂CH₂0) n- (Ci to C₂₀) Alkyl with n = 1 to 30,

0017R and R^a represent a hydrogen atom or one of the two radicals

0018Hydrogen atom and the other for a methyl group

0019and

0020at least one second crosslinked anionic copolymer comprising at least one crosslinking polysiloxane structural unit and at least one structural unit of the formula (IV)

0021<img file="WO2011069786A2_D0002.tif" />

0022or a group ^*- (CH₂CH₂0)_n- (Ci to C₂₀) Alkyl with n = 1 to 30,

0023G represents a direct bond or a carbonyl group,

0024R⁸ and R^! represent a hydrogen atom or one of the two radicals

0025Hydrogen atom and the other for a methyl group.

0026According to the formulas above and all the following formulas there is a chemical bond with the symbol ^* is characterized for a "free valence" of the corresponding structural fragment. Further structural fragments bind to this "free valence" in the corresponding copolymer. These are previously described and optionally additional structural fragments of the respective polymer.

0027Fixing polymers contribute to the hold and / or build-up of the hair volume and fullness of the overall hairstyle. At the same time, these polymers are also film-forming polymers and therefore generally typical substances for shaping hair treatment agents such as hair setting agents, hair foams, hair waxes, hair sprays. The film formation can be selective and only connect a few fibers. The so-called curl retention test is often used as a test method for the setting effect of a polymer.

0028Film-forming polymers are understood to mean those polymers which, on drying, leave a continuous film on the skin, hair or nails. Such film formers can be used in a wide variety of cosmetic products such as, for example, face masks, make-up, hair fixatives, hair sprays, hair gels, hair waxes, hair treatments, shampoos or nail varnishes. Polymers which have sufficient solubility in water or water / alcohol mixtures to be present in the agent according to the invention in completely dissolved form are particularly preferred. The film-forming polymers can be of synthetic or natural origin.

0029According to the invention, film-forming polymers are furthermore understood to mean those polymers which, when used in 0.01 to 20% by weight aqueous, alcoholic or aqueous-alcoholic solution, are able to deposit a transparent polymer film on the hair.

0030In the context of the invention, “crosslinked” or “crosslinking” is to be understood to mean the linking of polymer chains to one another by covalent chemical bonding to form a network. This polymer chain is covalently linked by a bridging polysiloxane molecular fragment. The crosslinking polysiloxane molecular fragment binds to the polymer chains bridged by the molecular fragment in each case by means of covalent chemical bonding.

0031An anionic polymer is understood according to the invention to mean a polymer which, in a protic solvent and under standard conditions, bears structural units with anionic groups which have to be compensated for by counterions while maintaining electroneutrality and does not have any structural units with permanently cationic or cationizable groups. Anionic groups include carboxyl and sulfonic acid groups.

0032The agent according to the invention preferably contains the first setting anionic copolymer in an amount of from 0.01 to 29.99% by weight, particularly preferably from 0.1 to 14.9% by weight, very particularly preferably from 0.1 to 9.5% by weight. -%, and most preferably from 0.2 to 5.0 wt .-%, each based on the weight of the total ready-to-use agent. The agent according to the invention contains the second crosslinked anionic copolymer preferably in an amount of 0.01 to 29.99% by weight, particularly preferably from 0.1 to 14.9% by weight, very particularly preferably from 0.1 to 9.5% by weight. -%, and most preferably from 0.2 to 5.0 wt .-%, each based on the weight of the total ready-to-use agent.

0033In addition, it has proven to be preferred if the agent according to the invention has a total amount of setting polymers of from 0.01 to 30% by weight, particularly preferably from 0.1 to 15% by weight, very particularly preferably from 0.5 to 10 , 0% by weight, most preferably from 1.0 to 6.0% by weight, in each case based on the weight of the total ready-to-use agent.

0034Preferred first setting anionic copolymers comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (IIa) and at least one structural unit of the formula (IIb) and at least one structural unit of the formula (III)

0035<img file="WO2011069786A2_D0003.tif" />

0036wherein

0037R represents a hydrogen atom or a methyl group,

0038R² represents a hydrogen atom or a methyl group

0039R³ stands for a (C-ι to C₂o) alkyl group or a group ^*- (CH₂CH₂0) n- (Ci to C₂o) -alkyl with n = 1 to 30,

0040R² represents a hydrogen atom or a methyl group

0041R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0042R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group.

0043Agents according to the invention which have at least one or more of the following features for the first setting anionic copolymer have been found to be particularly suitable:

0044- The radical R according to formula (I) preferably represents a hydrogen atom.

0045- R is preferably³ according to formula (II) (or R³ according to formula (IIa) and R³ according to formula (IIb) independently of one another) for a methyl group, ethyl group, 2-hydroxyethyl group, 2,3-dihydroxypropyl group, n-propyl group, isopropyl group, n-butyl group,

0046sec-butyl group or tert-butyl group.

0047- R is preferably³ according to formula (IIa) for a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or tert-butyl group.

0048- R is preferably³ according to formula (IIb) for a 2-hydroxyethyl group or 2,3-dihydroxypropyl group.

0049- R is preferably⁴ according to formula (III) for a hydrogen atom.

0050Preference is therefore given to agents according to the invention which, in addition to said second crosslinked anionic copolymer, contain at least one first setting anionic copolymer in a cosmetically acceptable carrier, comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (II) and at least one structural unit of the formula (III)

0051<img file="WO2011069786A2_D0004.tif" />

0052wherein

0053R² represents a hydrogen atom or a methyl group

0054R³ stands for a (Ci to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group.

0055Furthermore, agents according to the invention have been found to be suitable, in which, in addition to said second crosslinked anionic copolymer, at least one first setting anionic copolymer is present, comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (IIa) and at least one structural unit of the Formula (IIb) and at least one structural unit of the formula (III)

0056<img file="WO2011069786A2_D0005.tif" />

0057wherein

0058R² represents a hydrogen atom or a methyl group

0059R³ stands for a (Ci to C₂o) alkyl group,

0060R² represents a hydrogen atom or a methyl group

0061R³ stands for a (C₂ to C₄) -Hydroxyalkyl group (in particular 2-hydroxyethyl or 2,3-dihydroxypropyl),

0062R⁵ represents a hydrogen atom or a methyl group. The amount of the structural units of the formula (I) correspondingly contained in the first setting anionic copolymer preferably corresponds to 30 to 60% by weight, particularly preferably 35 to 55% by weight, in each case based on the weight of the said polymer. This applies mutatis mutandis to all the embodiments described above and later.

0063The amount of the structural units of the formula (II) correspondingly contained in the first setting anionic copolymer (or the sum of the structural units of the formulas (IIa) and (IIb)) preferably corresponds to 1 to 50% by weight, particularly preferably 5 to 40% by weight. -%, very particularly preferably from 10 to 40 wt .-%, each based on the weight of said polymer. This applies mutatis mutandis to all the embodiments described above and later.

0064The amount of the structural units of the formula (III) correspondingly contained in the first setting anionic copolymer preferably corresponds to 5 to 50% by weight, particularly preferably 10 to 40% by weight, in each case based on the weight of the said polymer. This applies mutatis mutandis to all the embodiments described above and later.

0065The first anionic setting copolymer is particularly preferably an anionic copolymer which is prepared from monomers comprising monomers (a) and (b) and (c):

0066(a) styrene and / or alpha-methylstyrene (in particular styrene),

0067(b) at least one monomer selected from methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-propyl methacrylate .-Butyl methacrylate

0068(c) acrylic acid and / or methacrylic acid.

0069In a further embodiment, the first anionic setting copolymer is an anionic copolymer which is prepared from monomers comprising monomers (a) and (b1) and (b2) and (c):

0070(a) styrene and / or alpha-methylstyrene (in particular styrene),

0071(b1) at least one monomer selected from methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate,

0072(b2) 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate,

0073(c) acrylic acid and / or methacrylic acid.

0074An example of a preferred first anionic setting polymer is a polymer with the INCI name styrene / acrylates copolymer. The second anionic copolymer which is mandatory in the agent according to the invention in addition to the first fixing copolymer is crosslinked. It was found that the effect according to the invention was particularly pronounced when the bridging polysiloxane molecule fragment was derived from a polysiloxane, at the two chain ends of which at least one radically polymerizable functionality binds.

0075The second crosslinked anionic copolymer preferably has a molecular weight M._w from 35000 to 60000 g / mol.

0076The crosslinking polysiloxane structural unit is in the second crosslinked anionic copolymer in an amount of 0.1 to 50.0% by weight, in particular 0.1 to 40.0% by weight, in each case based on the weight of the polymer, contain. This applies mutatis mutandis to all the embodiments described above and later.

0077The amount of the structural units of the formula (IV) correspondingly contained in the second crosslinked anionic copolymer preferably corresponds to 30.0 to 99.4% by weight, particularly preferably 10 to 40% by weight, in each case based on the weight of the said polymer. This applies mutatis mutandis to all the embodiments described above and later.

0078The amount of the structural units of the formula (V) correspondingly contained in the second crosslinked anionic copolymer preferably corresponds to 0.5 to 14.0% by weight, particularly preferably 0.5 to 10.0% by weight, very particularly preferably 3.0 to 6.0 wt .-%, each based on the weight of said polymer. This applies mutatis mutandis to all the embodiments described above and later.

0079The second crosslinked anionic copolymer has proven to be particularly suitable, comprising at least one crosslinking polysiloxane structural unit of the formula (PS) and at least one structural unit of the formula (IV) and at least one structural unit of the formula (

0080<img file="WO2011069786A2_D0006.tif" />

0081R ° represents a hydrogen atom or a methyl group, R⁷ stands for a linear or branched (Ci to C₂o) alkyl group, linear or branched (C₂ to C₂o) acyl group, a (C₂ to C₆) Hydroxyalkyl group or a group ^*- (ΟΗ₂ΟΗ₂0)_η- (Οι to C₂₀) Alkyl with n = 1 to 30,

0082G represents a direct bond or a carbonyl group,

0083R⁸ and R⁹ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group,

0084R represents a hydrogen atom or a methyl group,

0085R ⁰, R ², R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (C-ι to C₁₈) - alkoxy group (especially methoxy or ethoxy),

0086m represents an integer from 1 to 3

0087p represents an integer from 10 to 1000,

0088X stands for a direct bond or any molecular fragment.

0089According to formula (PS), X particularly preferably represents a direct bond, a methylene group, ethane-1,2-diyl, a group ^*-CO-0- (CH₂)_x-^* where x is 2 or 3 or a group ^*-CO- NH- (CH₂)_X-^* where x is 2 or 3.

0090Si-C-bonded in the sense of the invention means that the said hydrocarbon residue binds to the silicone structural fragment according to formula (PS) via a covalent silicon-carbon bond. m according to formula (PS) is preferably 1.

0091R ⁰ according to formula (PS) preferably represents a methyl group.

0092R ² and R ³ according to formula (PS) are preferably a methyl group.

0093It is preferred according to the invention to select the polysiloxane structural unit from:

(PS-1)

0095<img file="WO2011069786A2_D0007.tif" /><img file="WO2011069786A2_D0008.tif" />

0096where p is an integer from 10 to 1000.

0097Very particularly preferred polysiloxane structural units are selected from formula (PS-1), (PS-2), (PS-3) (most preferably of formula (PS-1)).

0098Agents according to the invention which have at least one or more of the following features for the second crosslinked anionic copolymer have been found to be particularly suitable:

0099According to formula (IV), G preferably represents a carbonyl group, R⁶ for a hydrogen atom or a methyl group and R⁷ for a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group.

0100According to formula (IV), G preferably represents a direct bond, R⁶ for a hydrogen atom and R² for an acetyl group, a propionyl group, a branched (C₈ to Ci₈) Alkanoyl group (especially a (C₈ to Ci₈) -soalkanoyl group, more preferably a (C₈ to d₂) -soalkanoyl group, for example isooctadecanoyl group, isononanoyl group or a neodecanoyl group).

0101R is preferably⁸ according to formula (V) for a methyl group and R⁹ stands for a hydrogen atom.

0102Preference is therefore given to agents according to the invention which, in addition to said first setting anionic copolymer, contain at least one second crosslinked anionic copolymer in a cosmetically acceptable carrier, comprising at least one structural unit of the formula (PS) and at least one structural unit of the formula (IV-1) and at least one a structural unit of the formula (V-1) <img file="WO2011069786A2_D0009.tif" />

0103R represents a hydrogen atom or a methyl group,

0104RR ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group with 1 to 18

0105Carbon atoms (especially methyl or phenyl) or a (Ci to d₈)-

0106Alkoxy group (especially methoxy or ethoxy),

0107m represents an integer from 1 to 3

0108P represents an integer from 10 to 1000,

0109X stands for a direct bond or any molecular fragment,

0110R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to C₁₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

0111The aforementioned preferred meanings of the groups R ⁰, R, R ², R ³ or m, p, and X apply mutatis mutandis.

0112Agents according to the invention are preferably suitable in which, in addition to said first setting anionic copolymer, contain in a cosmetically acceptable carrier at least one second crosslinked anionic copolymer comprising at least one structural unit of the formula (PS-6) and at least one structural unit of the formula (IV-1) and at least one structural unit of the formula (V-1)

0113<img file="WO2011069786A2_D0010.tif" />

0114wherein

0115p represents an integer from 10 to 1000,

0116R independently of one another represents a hydrogen atom or a methyl group, R represents a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

0117Furthermore, agents according to the invention have been found to be particularly suitable in which, in addition to said first setting anionic copolymer, in a cosmetically acceptable carrier comprise at least one second crosslinked anionic copolymer comprising at least one structural unit of the formula (PS-1) and at least one structural unit of the formula IV -1) and at least one structural unit of the formula (V-1)

0118<img file="WO2011069786A2_D0011.tif" /> represents an integer from 10 to 1000,

0119stands for a linear or branched (C₂ to Ci₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

0120The second anionic crosslinked copolymer is particularly preferably an anionic copolymer which is prepared from monomers comprising monomers (d) and (e) and (f):

0121(d) alpha, omega-divinylpolydimethylsiloxane of the formula

0122H₂C = CH-SiMe₂-0- (SiMe₂-0-)_p-SiMe₂-CH = CH₂ with p = 10 to 1000,

0123(e) at least one monomer selected from vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl isononanoate,

0124(f) crotonic acid and / or acrylic acid and / or methacrylic acid (especially crotonic acid).

0125In a further embodiment, the second crosslinked anionic copolymer is an anionic copolymer which is prepared from monomers comprising monomers (d) and (e1) and (e2) and (f):

0126(d) alpha, omega-divinylpolydimethylsiloxane of the formula

0127H₂C = CH-SiMe₂-0- (SiMe₂-0-)_p-SiMe₂-CH = CH₂ with p = 10 to 1000,

0128(e1) at least one monomer selected from vinyl acetate, vinyl propionate

0129(e2) at least one monomer selected from vinyl neodecanoate, vinyl isononanoate, (f) crotonic acid and / or acrylic acid and / or methacrylic acid (especially crotonic acid).

0130The second anionic crosslinked copolymers according to the invention are, for example, under the trade name Wacker Belsil^® P101 available from Wacker Chemie AG. Agents (A) to (L) mentioned below are mentioned as examples of very particularly suitable agents according to the invention:

(A):

0132Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0133at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (II) and at least one structural unit of the formula (III) <img file="WO2011069786A2_D0012.tif" /> wherein

0134R² represents a hydrogen atom or a methyl group

0135R³ stands for a (C-ι to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group.

0136and

0137at least one second crosslinked anionic copolymer comprising at least one crosslinking polysiloxane structural unit of the formula (PS) and at least one structural unit purity of the formula (V)

0138<img file="WO2011069786A2_D0013.tif" /> represents a hydrogen atom or a methyl group,

0139R⁷ stands for a linear or branched (C-ι to C₂o) alkyl group, linear or branched (C₂ to C₂₀) Acyl group, a (C₂ to C₆) Hydroxyalkyl group or a group<img file="WO2011069786A2_D0014.tif" /> to C₂₀) Alkyl with n = 1 to 30,

0140G represents a direct bond or a carbonyl group,

0141R⁸ and R^£ represent a hydrogen atom or one of the two radicals

0142Hydrogen atom and the other for a methyl group,

0143R 'represents a hydrogen atom or a methyl group,

014412

0145R¹⁰, RR ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈)-

0146Alkoxy group (especially methoxy or ethoxy),

0147m represents an integer from 1 to 3

0148P represents an integer from 10 to 1000,

0149X stands for a direct bond or any molecular fragment.

(B):

0151Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0152at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (II) and at least one structural unit of the formula (III) <img file="WO2011069786A2_D0015.tif" /> wherein

0153R represents a hydrogen atom or a methyl group

0154R³ stands for a (Ci to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group.

0155and

0156at least one second crosslinked anionic copolymer comprising at least one structural unit of the formula (PS) and at least one structural unit of the formula (IV-1) and at least one structural unit of the formula (V-1)

0157<img file="WO2011069786A2_D0016.tif" />

0158R 'represents a hydrogen atom or a methyl group,

0159R 'R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to Ci₈) - alkoxy group (especially methoxy or ethoxy),

0160m represents an integer from 1 to 3

0161P represents an integer from 10 to 1000,

0162X stands for a direct bond or any molecular fragment, R stands for a linear or branched (C₂ to d₈) Acyl group (especially for

0163(C.₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(C):

0165Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0166at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (II) and at least one structural unit of the formula (III)

0167<img file="WO2011069786A2_D0017.tif" />

0168wherein

0169R² represents a hydrogen atom or a methyl group

0170R³ stands for a (C-ι to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group.

0171and

0172at least one second crosslinked anionic copolymer comprising at least one structural unit of the formula (PS-1) and at least one structural unit of the

0173<img file="WO2011069786A2_D0018.tif" />

0174wherein

0175p represents an integer from 10 to 1000,

0176R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(D):

0178Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0179at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (IIa) and at least one structural unit of the formula (IIb) and at least one structural unit of the formula (III) <img file="WO2011069786A2_D0019.tif" />

0180wherein

0181R represents a hydrogen atom or a methyl group,

0182R² represents a hydrogen atom or a methyl group

0183R³ stands for a (C-ι to C₂o) alkyl group or a group * - (CH₂CH₂0) n- (Ci to C₂o) -alkyl with n = 1 to 30,

0184R² represents a hydrogen atom or a methyl group

0185R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0186R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0187and

0188at least one second crosslinked anionic copolymer comprising at least one crosslinking polysiloxane structural unit of the formula (PS) and at least one structural unit purity of the formula (V)

0189<img file="WO2011069786A2_D0020.tif" />

0190R represents a hydrogen atom or a methyl group,

0191R⁷ stands for a linear or branched (Ci to C₂o) alkyl group, linear or branched (C₂ to C₂₀) Acyl group, a (C₂ to C₆) Hydroxyalkyl group or a group<img file="WO2011069786A2_D0021.tif" /> to C₂₀) Alkyl with n = 1 to 30,

0192G represents a direct bond or a carbonyl group,

0193R⁸ and R^£ represent a hydrogen atom or one of the two radicals

0194Hydrogen atom and the other for a methyl group,

0195represents a hydrogen atom or a methyl group,

0196R¹⁰, R¹², R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈) - alkoxy group (especially methoxy or ethoxy),

0197m represents an integer from 1 to 3

0198P stands for an integer from 1 0 to 1000, X stands for a direct bond or any molecular fragment.

(E):

0200Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0201at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (IIa) and at least one structural unit of the formula (IIb) and at least one structural unit of the

0202<img file="WO2011069786A2_D0022.tif" />

0203wherein

0204R represents a hydrogen atom or a methyl group,

0205R² represents a hydrogen atom or a methyl group

0206R³ stands for a (C-ι to C₂o) alkyl group or a group * - (CH₂CH₂0) n- (Ci to C₂o) -alkyl with n = 1 to 30,

0207R² represents a hydrogen atom or a methyl group

0208R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0209R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0210and

0211at least one second crosslinked anionic copolymer comprising at least one structural unit of the formula (PS) and at least one structural unit of the formula (IV-1) and at least one structural unit of the formula (V-1)

0212<img file="WO2011069786A2_D0023.tif" />

0213R 'represents a hydrogen atom or a methyl group,

0214R 'R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈) - alkoxy group (especially methoxy or ethoxy),

0215m represents an integer from 1 to 3, P represents an integer from 10 to 1000,

0216X stands for a direct bond or any molecular fragment,

0217R stands for a linear or branched (C₂ to C₁₈) Acyl group (especially for

0218(C.₈ to C₁₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(F):

0220Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0221at least one first setting anionic copolymer comprising at least one structural unit of the formula (I) and at least one structural unit of the formula (IIa) and at least one structural unit of the formula (IIb) and at least one structural unit of the

0222<img file="WO2011069786A2_D0024.tif" />

0223wherein

0224R represents a hydrogen atom or a methyl group,

0225R² represents a hydrogen atom or a methyl group

0226R³ stands for a (Ci to C2o) alkyl group or a group * - (CH₂CH₂0)_n- (Ci to C2o) -alkyl with n = 1 to 30,

0227R² represents a hydrogen atom or a methyl group

0228R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0229R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0230and

0231at least one second cross-linked anionic copolymer comprising at least one structural unit of the formula (PS-1) and at least one structural unit of the formula (IV-1) and at least one structural unit of the formula (V-1)

0232<img file="WO2011069786A2_D0025.tif" />

0233wherein

0234p represents an integer from 10 to 1000,

0235R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

0236(G): Agent for treating keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0237at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight of at least one structural unit of the formula (II) and 5 to 50 % By weight of at least one structural unit of the formula <img file="WO2011069786A2_D0026.tif" /> wherein

0238R² represents a hydrogen atom or a methyl group

0239R³ stands for a (Ci to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group

0240and

0241at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS) and 30 to 99.4% by weight of at least one structural unit of the

0242% of at least one structural unit of the formula (V)

0243<img file="WO2011069786A2_D0027.tif" />

0244R represents a hydrogen atom or a methyl group,

0245R⁷ stands for a linear or branched (Ci to C₂o) alkyl group, linear or branched (C₂ to C₂₀) Acyl group, a (C₂ to C₆) Hydroxyalkyl group or a group<img file="WO2011069786A2_D0028.tif" /> to C₂₀) Alkyl with n = 1 to 30,

0246G represents a direct bond or a carbonyl group,

0247R⁸ and R^£ represent a hydrogen atom or one of the two radicals

0248Hydrogen atom and the other for a methyl group,

0249R¹¹ represents a hydrogen atom or a methyl group,

0250R¹⁰, R¹², R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈) - alkoxy group (especially methoxy or ethoxy), m represents an integer from 1 to 3

0251P represents an integer from 10 to 1000,

0252X stands for a direct bond or any molecular fragment.

(H):

0254Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0255at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight of at least one structural unit of the formula (II) and 5 to 50 % By weight of at least one structural unit of the formula <img file="WO2011069786A2_D0029.tif" /> wherein

0256R² represents a hydrogen atom or a methyl group

0257R³ stands for a (Ci to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group

0258and

0259at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS) and 30 to 99.4% by weight of at least one structural unit of the formula ( IV-1) and 0.5 to 14.0% by weight of at least one structural unit of the formula (V-1)

0260<img file="WO2011069786A2_D0030.tif" />

0261R 'represents a hydrogen atom or a methyl group,

0262R 'R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈) - alkoxy group (especially methoxy or ethoxy),

0263m represents an integer from 1 to 3

0264P represents an integer from 10 to 1000,

0265X stands for a direct bond or any molecular fragment, R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(I):

0267Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0268at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight of at least one structural unit of the formula (II) and 5 to 50 % By weight of at least one structural unit of the formula (III) <img file="WO2011069786A2_D0031.tif" /> wherein

0269R² represents a hydrogen atom or a methyl group

0270R³ stands for a (C-ι to C₂o) alkyl group, or a (C₂ to C₆) Hydroxyalkyl group, and R⁵ represents a hydrogen atom or a methyl group

0271and

0272at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS-1) and 30 to 99.4% by weight of at least one structural unit of the Formula (IV-1) and 0.5 to 14.0% by weight of at least one structural unit of the formula (V-1)

0273<img file="WO2011069786A2_D0032.tif" /> (V-1) wherein

0274p represents an integer from 10 to 1000,

0275R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(J):

0277Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0278at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight in total of at least one structural unit of the formula (IIa) and ( IIb) and 5 to 50% by weight of at least one structural unit of the formula (III) <img file="WO2011069786A2_D0033.tif" />

0279wherein

0280R represents a hydrogen atom or a methyl group,

0281R² represents a hydrogen atom or a methyl group

0282R³ stands for a (C-ι to C₂o) alkyl group or a group * - (CH₂CH₂0) n- (Ci to C₂o) -alkyl with n = 1 to 30,

0283R² represents a hydrogen atom or a methyl group

0284R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0285R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0286and

0287at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS) and 30 to 99.4% by weight of at least one structural unit of the formula IV -1) and 0.5 to 14.0% by weight of at least one structural unit of the formula (V-1)

0288<img file="WO2011069786A2_D0034.tif" />

0289R represents a hydrogen atom or a methyl group,

0290R⁷ stands for a linear or branched (Ci to C₂o) alkyl group, linear or branched (C₂ to C₂₀) Acyl group, a (C₂ to C₆) Hydroxyalkyl group or a group<img file="WO2011069786A2_D0035.tif" /> to C₂₀) Alkyl with n = 1 to 30,

0291G represents a direct bond or a carbonyl group,

0292R⁸ and R^£ represent a hydrogen atom or one of the two radicals

0293Hydrogen atom and the other for a methyl group,

0294R 'represents a hydrogen atom or a methyl group,

029512

0296R¹⁰, RR ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈) - alkoxy group (especially methoxy or ethoxy),

0297m represents an integer from 1 to 3, P represents an integer from 10 to 1000,

0298X stands for a direct bond or any molecular fragment.

(K):

0300Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0301at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight in total of at least one structural unit of the formula (IIa) and ( IIb) and 5 to 50% by weight of at least one structural unit of the formula (III)

0302<img file="WO2011069786A2_D0036.tif" />

0303wherein

0304R represents a hydrogen atom or a methyl group,

0305R² represents a hydrogen atom or a methyl group

0306R³ stands for a (Ci to C2o) alkyl group or a group * - (CH₂CH₂0)_n- (Ci to C2o) -alkyl with n = 1 to 30,

0307R² represents a hydrogen atom or a methyl group

0308R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0309R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0310and

0311at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS) and 30 to 99.4% by weight of at least one structural unit of the formula ( IV-1) and 0.5 to 14.0% by weight of at least one structural unit of the formula (V-1)

0312<img file="WO2011069786A2_D0037.tif" />

0313R 'represents a hydrogen atom or a methyl group,

0314R 'R ³ independently of one another represent a monovalent, Si-C-bonded, optionally substituted hydrocarbon group having 1 to 18 carbon atoms (in particular methyl or phenyl) or a (Ci to d₈)-

0315Alkoxy group (especially methoxy or ethoxy),

0316m represents an integer from 1 to 3

0317P represents an integer from 10 to 1000,

0318X stands for a direct bond or any molecular fragment,

0319R stands for a linear or branched (C₂ to Ci₈) Acyl group (especially for

0320(C.₈ to Ci₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

(L):

0322Agent for the treatment of keratin fibers, in particular human hair, contained in a cosmetically acceptable carrier

0323at least one first setting anionic copolymer, each comprising 30 to 60% by weight, based on the weight of the polymer, of at least one structural unit of the formula (I) and 1 to 50% by weight in total of at least one structural unit of the formula (IIa) and ( IIb) and 5 to 50% by weight of at least one structural unit of the formula (III)

0324<img file="WO2011069786A2_D0038.tif" />

0325wherein

0326R represents a hydrogen atom or a methyl group,

0327R² represents a hydrogen atom or a methyl group

0328R³ stands for a (Ci to C2o) alkyl group or a group * - (CH₂CH₂0)_n- (Ci to C2o) -alkyl with n = 1 to 30,

0329R^2* represents a hydrogen atom or a methyl group

0330R³ stands for a (C₂ to C₆) Hydroxyalkyl group,

0331R⁴ and R⁵ stand for a hydrogen atom or one of the two radicals for a hydrogen atom and the other for a methyl group

0332and

0333at least one second crosslinked anionic copolymer comprising in each case, based on the weight of the polymer, 0.1 to 50% by weight of at least one crosslinking polysiloxane structural unit of the formula (PS-1) and 30 to 99.4% by weight of at least one structural unit of the Formula (IV-1) and 0.5 to 14.0% by weight of at least one structural unit of the formula (V-1)

0334<img file="WO2011069786A2_D0039.tif" />

0335where p is an integer from 10 to 1000,

0336R stands for a linear or branched (C₂ to d₈) Acyl group (especially for (C₈ to C₁₂) -soalkanoyl, isononanoyl, neodecanoyl, acetyl, propionyl).

0337All of the preferred parameters mentioned above also apply mutatis mutandis to the particularly suitable embodiments (A) to (L) mentioned by way of example.

0338The agents according to the invention contain the ingredients or active ingredients in a cosmetically acceptable carrier.

0339Preferred cosmetically acceptable carriers are aqueous, alcoholic or aqueous-alcoholic media with preferably at least 10% by weight of water, based on the total composition. In particular, the lower alcohols with 1 to 4 carbon atoms usually used for cosmetic purposes, such as ethanol and isopropanol, can be included as alcohols.

0340In the context of a preferred embodiment of the agent according to the invention, the agent therefore additionally contains at least one alcohol which has 2 to 6 carbon atoms and 1 to 3 hydroxyl groups. This additional alcohol is in turn preferably selected from at least one compound from the group which is formed from ethanol, ethylene glycol, isopropanol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, n-butanol, 1, 3-butylene glycol. A very particularly preferred alcohol is ethanol.

0341The additional alcohol with 2 to 6 carbon atoms and 1 to 3 hydroxyl groups is preferred in the agent according to the invention (in particular in the presence of at least one blowing agent) in an amount of 40% by weight to 65% by weight, in particular 40% by weight. up to 50 wt .-%, each based on the weight of the cosmetic composition.

0342Organic solvents or a mixture of solvents with a boiling point below 400 ° C. can be present as additional co-solvents in an amount of 0.1 to 15 percent by weight, preferably 1 to 10 percent by weight, based on the total agent. Unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane are particularly suitable as additional co-solvents. Further, particularly preferred water-soluble solvents are polyethylene glycol and propylene glycol in an amount of up to 30% by weight, based on the total agent.

0343In particular, the addition of propylene glycol and / or polyethylene glycol and / or polypropylene glycol increases the flexibility of the polymer film formed when the agent according to the invention is used. If a flexible hold is desired, the agents according to the invention preferably contain 0.01 to 30% by weight of polyethylene glycol and / or polypropylene glycol based on the entire agent.

0344The agents preferably have a pH of 2 to 11. The pH range between 2 and 8 is particularly preferred. For the purposes of this document, the information on the pH value relates to the pH value at 25 ° C., unless stated otherwise.

0345The effects according to the invention are obtained by adding at least one (C₂ to C₆) - Increase trialkyl citrate to the agent according to the invention. It is therefore preferred according to the invention if the agents additionally contain at least one compound of the formula (E)<img file="WO2011069786A2_D0040.tif" />

0346wherein

0347R, R² and R³ independently for a (C₂ to C₆) Alkyl group.

0348Examples of a (C₂ to C₆) -Alkyl group according to formula (E) are methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl.

0349Triethyl citrate has been found to be a particularly preferred compound of the formula (E).

0350The agent according to the invention preferably contains the compounds of formula (E) in an amount of 0.01 to 1% by weight, in particular 0.05 to 0.3% by weight, in each case based on the weight of the total agent.

0351The agents according to the invention preferably additionally contain at least one surfactant, non-ionic, anionic, cationic, ampholytic surfactants being particularly suitable. The group of ampholytic or amphoteric surfactants includes zwitterionic surfactants and ampholytes. According to the invention, the surfactants can already have an emulsifying effect. The use of at least one nonionic surfactant and / or at least one cationic surfactant is preferred in the context of this embodiment of the invention.

0352The additional surfactants in the agent according to the invention are preferably present in an amount of from 0.01% by weight to 5% by weight, particularly preferably from 0.05% by weight to 0.5% by weight, based in each case on the Weight of the agent included.

0353It has proven to be particularly preferred if the agents according to the invention additionally contain at least one nonionic surfactant. Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Such connections are, for example

0354Addition products of 2 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group ,

0355with a methyl or C₂ - C₆ - Addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide which are end group-capped to linear and branched fatty alcohols with 8 to 30 C atoms, to fatty acids with 8 to 30 C atoms and to alkylphenols with 8 to 15 C atoms in the alkyl group, such as those sold under the trade names Dehydol^® LS, dehydol^® LT (Cognis) available types,

0356Ci2-C₃₀Fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

0357Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

0358Polyol fatty acid esters, such as the commercial product Hydagen^® HSP (Cognis) or

0359Sovermol types (Cognis),

0360alkoxylated triglycerides,

0361alkoxylated fatty acid alkyl esters of the formula (Tl)

0362R CO- (OCH₂CHR²)_wOR³ (Tl)

0363in the R CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R² for hydrogen or methyl, R³ represents linear or branched alkyl radicals having 1 to 4 carbon atoms and w represents numbers from 1 to 20,

0364Amine oxides,

0365Hydroxy mixed ethers as described, for example, in DE-OS 19738866, sorbitan fatty acid esters and addition products of ethylene oxide with sorbitan fatty acid esters such as, for example, the polysorbates,

0366Sugar fatty acid esters and adducts of ethylene oxide with sugar fatty acid esters, adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,

0367Sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (Tl I),

0368R⁴0- [G]_p (T-Il)

0369in the R⁴ represents an alkyl or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. The preferred alkyl and / or alkenyl oligoglycosides are alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (T-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides is on and stands for a number between 1 and 10. While p in the individual molecule must always be an integer and here can take on the values ​​p = 1 to 6, the value p is one for a certain alkyl oligoglycoside analytically determined arithmetic size, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

0370The alkylene oxide adducts with saturated linear fatty alcohols and fatty acids, each with 2 to 100 moles of ethylene oxide per mole of fatty alcohol or fatty acid, have proven to be very particularly preferred nonionic surfactants. Preparations with excellent properties are also obtained if they are used as nonionic surfactants Ci₂-C₃₀- Contain fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol and / or adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

0371For the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

0372The agents according to the invention very particularly preferably contain at least one addition product of 15 to 100 mol of ethylene oxide, in particular of 15 to 50 mol of ethylene oxide, with a linear or branched (in particular linear) fatty alcohol having 8 to 22 carbon atoms. It is very particularly preferably ceteareth-15, ceteareth-25 or ceteareth-50, which as eumulgin^® CS 15 (COGNIS), Cremophor A25 (BASF SE) or Eumulgin^® CS 50 (COGNIS) are marketed.

0373In principle, all anionic surface-active substances suitable for use on the human body are suitable as anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group,

0374linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

0375Ether carboxylic acids of the formula R-0- (CH2-CH20) x-CH2-COOH, in which R is a linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16,

0376Acyl sarcosides with 8 to 24 carbon atoms in the acyl group,

0377Acyl taurides with 8 to 24 carbon atoms in the acyl group,

0378Acyl isethionates with 8 to 24 carbon atoms in the acyl group,

0379Sulfosuccinic acid mono- and dialkyl esters with 8 to 24 carbon atoms in the alkyl group and

0380Sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,

0381linear alkane sulfonates with 8 to 24 carbon atoms,

0382linear alpha olefin sulfonates with 8 to 24 carbon atoms,

0383Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 carbon atoms,

0384- Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH₂-CH₂0)_x-OS0₃H, in which R is a preferably linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates,

0385sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers,

0386Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds, esters of tartaric acid and citric acid with alcohols, which are the products of the addition of about 2-15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols with 8 to 22 carbon atoms,

0387Alkyl and / or alkenyl ether phosphates of the formula (TV),

O II

0389R¹(OCH₂CH₂)_n - 0 - p -OR²

0390I.

0391^0X (TV)

0392in which R is preferred for an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R² for hydrogen, a residue (CH₂CH₂0)_nR or X, n for numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal or NR³R⁴R⁵R⁶, with R³ to R⁶ independently of one another represents hydrogen or a C1 to C4 hydrocarbon radical,

0393sulfated fatty acid alkylene glycol esters of the formula (T-VI)

0394R⁷CO (AlkO)_nS0₃M (T-Vl) in the R⁷CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, alk for CH₂CH₂, CHCH₃CH₂ and / or CH₂CHCH₃, n stands for numbers from 0.5 to 5 and M stands for a cation,

0395Amide ether carboxylic acids,

0396Condensation products from C₈ - C₃₀ - Fatty alcohols with protein hydrolyzates and / or amino acids and their derivatives, which are known to the person skilled in the art as protein fatty acid condensates, such as, for example, the Lamepon^® - Guys, Gluadin^® - Types, Hostapon^® KCG or the Amisoft^® - guys.

0397Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines can also be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyl trimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides. The long alkyl chains of these surfactants preferably have 10 to 18 carbon atoms, such as. B. in cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further preferred cationic surfactants are the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.

0398Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO in the molecule^&lt;_) - or -S0₃^&lt;_) -Carry group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the coconut-acylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

0399Ampholytes are understood to mean those surface-active compounds which, in addition to a C₈ - C₂4th - Alkyl or acyl group in the molecule at least one free amino group and at least one -COOH- or -S0₃Contain H group and are capable of forming internal salts. Examples of suitable ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 24 C atoms in the alkyl group. Particularly preferred ampholytes are the N-cocoalkylaminopropionate, the cocoacylaminoethylaminopropionate and the C12-Ci₈ - acylsarcosine. The agents according to the invention can optionally additionally contain at least one film-forming polymer and / or setting polymer. These additional polymers are different from the first film-forming anionic copolymer and the second cross-linked anionic copolymer. The optionally added film-forming and / or setting polymers are preferably cationic and / or nonionic.

0400According to the invention, the cationic film-forming and / or cationic setting polymers can be selected from cationic, quaternized cellulose derivatives.

0401In general, those cationic, quaternized celluloses which have more than one permanent cationic charge in a side chain prove to be advantageous in the sense of the invention.

0402Among the cationic cellulose derivatives, those which are produced from the reaction of hydroxyethyl cellulose with a dimethyldiallylammonium reactant (in particular dimethyldiallylammonium chloride), if appropriate in the presence of further reactants, are to be emphasized. Of these cationic celluloses, those cationic celluloses with the INCI name Polyquaternium-4 are particularly suitable which, for example, have the name Celquat^® H 100, Celquat^® L 200 are sold by National Starch.

0403Such cationic film-forming and / or cationic setting polymers are furthermore suitable which comprise at least one structural unit of the formula (Ml) and at least one structural unit of the formula (M-VI) and optionally at least one structural unit of the formula (MV)

0404<img file="WO2011069786A2_D0041.tif" />

0405wherein

0406R and R⁴ independently represent a hydrogen atom or a methyl group,

0407A and A² independently of one another represent a group of ethane-1, 2-diyl, propane-1, 3-diyl or

0408Butane-1,4-diyl,

0409RR²²,, RR³³,, RR⁵⁵ and R⁶ stand independently for one (Ci to C₄) Alkyl group,

0410R⁷ stands for a (C₈ to C₃₀) Alkyl group. All possible physiologically compatible anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate, are used to compensate for the positive charge of the monomer (M-VI).

0411Suitable compounds are, for example, as

0412Copolymers of dimethylaminoethyl methacrylate quaternized with diethyl sulfate, with vinyl pyrrolidone with the INCI name Polyquaternium-1 1 under the names Gafquat^® 440, Gafquat^®734, Gafquat^®755 (each from ISP) and Luviquat PQ 1 1 PN (from BASF SE),

0413Copolymers of methacryloylaminopropyllauryldimethylammonium chloride with vinylpyrrolidone and dimethylaminopropylmethacrylamide with the INCI name Polyquaternium-55 under the trade names, Styleze^® W-10, Styleze^® W-20 (company ISP),

0414Copolymers of N-vinylpyrrolidone, N-vinylcaprolactam, N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-69) under the trade name AquaStyle^® 300 (28-32% by weight of active substance in ethanol-water mixture) (company ISP)

0415available in the stores.

0416As film-forming and / or setting polymers which can be used with particular preference in the sense of the invention, selected from cationic polymers which contain at least one structural unit which have a permanently cationized nitrogen atom, such cationic film-forming and / or cationic setting polymers which have at least one structural element of the formula ( M1) included

0417<img file="WO2011069786A2_D0042.tif" /> "(M1)

0418wherein

0419R for a (Ci to C₄) Alkyl group, in particular a methyl group,

0420and additionally have at least one further cationic and / or nonionic structural element.

0421All possible physiologically compatible anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate, are used to compensate for the positive polymer charge of the component. It is again preferred according to the invention if at least one copolymer (b1) is present in the powdery composition according to the invention as the cationic film-forming and / or cationic setting polymer of this embodiment, which comprises at least h a structural element of the formula (MI)

0422<img file="WO2011069786A2_D0043.tif" />

0423wherein

0424R for a (Ci to C₄) Alkyl group, especially a methyl group.

0425All possible physiologically compatible anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate, are used to compensate for the positive polymer charge of the copolymers (b1).

0426Very particularly preferred cationic film-forming and / or cationic setting polymers as copolymers (b1) contain 10 to 30 mol%, preferably 15 to 25 mol% and in particular 20 mol% of structural units of the formula (M1) and 70 to 90 mol %, preferably 75 to 85 mol% and in particular 80 mol% of structural units according to formula (M-I)

0427It is particularly preferred here if the copolymers (b1) in addition to polymer units which result from the incorporation of the structural units of the formula (M1) and (Ml) mentioned in the copolymer, at most 5% by weight, preferably at most 1% by weight, Contain polymer units that go back to the incorporation of other monomers. The copolymers (b1) are preferably composed exclusively of structural units of the formula (M1) with R "= methyl and (Ml) and can be represented by the general formula (polyl)

0428<img file="WO2011069786A2_D0044.tif" />

0429^{CH; 3} (Polyl)

0430describe, the indices m and p vary depending on the molecular weight of the polymer and should not mean that it is block copolymers. Rather, structural units of the formula (M1) and of the formula (Ml) can be statistically distributed in the molecule. If a chloride ion is used to compensate for the positive charge of the polymer of the formula (polyl), these N-methylvinylimidazole / vinylpyrrolidone copolymers are referred to as Polyquaternium-16 according to the INCI nomenclature and are, for example, from BASF under the trade name Luviquat^® Style, Luviquat^® FC 370, Luviquat^® FC 550, Luviquat^® FC 905 and Luviquat^® HM 552

0431If a methosulfate is used to compensate for the positive charge of the polymer of the formula (polyl), these N-methylvinylimidazole / vinylpyrrolidone copolymers are referred to as Polyquaternium-44 according to the INCI nomenclature and are, for example, from BASF under the trade name Luviquat^® UltraCare available.

0432In addition to the copolymer (s) (b1) or in its place, powdery compositions according to the invention may also contain copolymers (b2) which, starting from the copolymer (b1), serve as additional structural units, structural units of the formula

0433<img file="WO2011069786A2_D0045.tif" />

0434Further particularly preferred powdery compositions according to the invention are thus characterized in that they contain as cationic film-forming and / or cationic setting polymer at least one copolymer (b2) which has at least one structural unit according to formula (M1-a) and at least one structural unit according to formula (Ml)

0435<img file="WO2011069786A2_D0046.tif" /> (M-ll).

0436It is also particularly preferred here if the copolymers (b2) in addition to polymer units which result from the incorporation of the structural units mentioned according to formula (M1-a), (Ml) and (M-II) into the copolymer, a maximum of 5% by weight , preferably a maximum of 1 wt .-%, contain polymer units that go back to the incorporation of other monomers. The copolymers (b2) are preferably composed exclusively of structural units of the formulas (M1-a), (Ml) and (M-II) and can be represented by the general formula (Poly2) <img file="WO2011069786A2_D0047.tif" />

0437describe, the indices m, n and p vary depending on the molecular weight of the polymer and should not mean that it is block copolymers. Rather, structural units of said formulas can be statistically distributed in the molecule.

0438All possible physiologically compatible anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate, are used to compensate for the positive polymer charge of component (b2).

0439If a methosulfate is used to compensate for the positive charge of the polymer of the formula (Poly2), such N-methylvinylimidazoleA / inylpyrrolidone / vinylcaprolactam copolymers are referred to as Polyquarternium-46 according to the INCI nomenclature and are, for example, from BASF under the trade name Luviquat^® Hold available.

0440Very particularly preferred copolymers (b2) contain 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units of the formula (M1-a) and 30 to 50 mol%, preferably 35 to 45 mol% and in particular 40 mol% of structural units according to formula (I) and 40 to 60 mol%, preferably 45 to 55 mol% and in particular 60 mol% structural units according to formula (M-II) .

0441In addition to the copolymer (s) (b1) and / or (b2) or on its or in their place, the powdery compositions according to the invention can also contain copolymers (b3) as the film-forming cationic and / or setting cationic polymer, which have structural units of the formulas (M1-a) and (I) as structural units, and further structural units from the group of vinylimidazole units and further structural units from the group of acrylamide and / or methacrylamide units.

0442Further particularly preferred powdery compositions according to the invention are characterized in that they contain as cationic film-forming and / or cationic setting polymer at least one copolymer (b3) which has at least one structural unit according to formula (M1-a) and at least one structural unit according to formula (Ml) and contains at least one structural unit according to formula (M-VIII) and at least one structural unit according to formula (M-VIII) <img file="WO2011069786A2_D0048.tif" /> (M-VIII) (M-VIII).

0443Here, too, it is particularly preferred if the copolymers (b3), in addition to polymer units which result from the incorporation of the structural units mentioned according to formula (M1-a), (Ml), (M-VIII) and (M-VIII) into the copolymer, contain a maximum of 5% by weight, preferably a maximum of 1% by weight, of polymer units which are based on the incorporation of other monomers. The copolymers (b3) are preferably exclusively composed of structural units of the formula (M1-a), (Ml), (M-Vll) my formula (Poly3)

0444<img file="WO2011069786A2_D0049.tif" />

0445³ (Poly3)

0446describe, the indices m, n, o and p vary depending on the molecular weight of the polymer and should not mean that it is block copolymers. Rather, structural units of the formulas (M1-a), (Ml), (M-VIII) and (M-VIII) can be statistically distributed in the molecule.

0447All possible physiologically compatible anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate, are used to compensate for the positive polymer charge of component (b2).

0448If a methosulfate is used to compensate for the positive charge of the polymer of the formula (Poly3), such N-methylvinylimidazole / vinylpyrrolidoneA / inylimidazole / methacrylamide copolymers are referred to as Polyquaternium-68 according to the INCI nomenclature and are, for example, from BASF under the trade name Luviquat^® Supreme available.

0449Very particularly preferred copolymers (b3) contain 1 to 12 mol%, preferably 3 to 9 mol% and in particular 6 mol% of structural units of the formula (M1-a) and 45 to 65 mol%, preferably 50 to 60 mol% and in particular 55 mol% of structural units according to formula (M- I) and 1 to 20 mol%, preferably 5 to 15 mol% and in particular 10 mol% of structural units according to formula (M- Vll) and 20 to 40 mol%, preferably 25 to 35 mol% and in particular 29 mol% of structural units of the formula (M-VIII). Among the additional film-forming cationic and / or setting polymer selected from the cationic polymers with at least one structural element of the above formula (M1), the following are preferred:

0450Vinyl pyrrolidone / 1-vinyl-3-methyl-1 H-imidazolium chloride copolymers (such as that with the INCI name Polyquaternium-16 under the trade names Luviquat^® Style, Luviquat^® FC 370, Luviquat^® FC 550, Luviquat^® FC 905 and Luviquat^® HM 552 (BASF SE)),

0451Vinyl pyrrolidone / 1-vinyl-3-methyl-1 H-imidazolium methyl sulfate copolymers (such as that with the INCI name Polyquaternium-44 under the trade names Luviquat^® Care (BASF SE)),

0452VinylpyrrolidonA inylcaprolactam / 1-vinyl-3-methyl-1 H-imidazolium terpolymer (such as that with the INCI name Polyquaternium-46 under the trade names Luviquat^® Care or Luviquat^® Hold (BASF SE)),

0453Vinyl pyrrolidone / methacrylamide aminimidazole / 1-vinyl-3-methyl-1 H-imidazolium methyl sulfate copolymer (such as that with the INCI name Polyquaternium-68 under the trade name Luviquat^® Supreme (BASF SE)), as well as mixtures of these polymers.

0454In a preferred embodiment, the powdered compositions according to the invention contain at least one film-forming nonionic and / or setting nonionic polymer as film-forming and / or setting polymer.

0455According to the invention, a nonionic polymer is understood to mean a polymer which, in a protic solvent under standard conditions, carries essentially no structural units with permanently cationic or anionic groups which have to be compensated for by counterions while maintaining electroneutrality. Cationic groups include, for example, quaternized ammonium groups, but no protonated amines. Anionic groups include, for example, carboxyl and sulfonic acid groups.

0456The film-forming nonionic and / or setting nonionic polymers in the agent according to the invention are preferably in an amount from 0.1% by weight to 20.0% by weight, particularly preferably from 0.2% by weight to 15.0% by weight .-%, very particularly preferably from 0.5 wt .-% to 5.0 wt .-%, each based on the weight of the powdered composition according to the invention.

0457The film-forming nonionic and / or setting nonionic polymers are in turn preferably selected from at least one polymer from the group that is formed from

0458Homopolymers and nonionic copolymers of N-vinylpyrrolidone,

0459nonionic copolymers of isobutene, nonionic copolymers of maleic anhydride.

0460A combination of film-forming nonionic and / or setting nonionic polymers is preferred, comprising at least one nonionic copolymer of maleic anhydride and at least one polymer from the group formed from homopolymers and nonionic copolymers of N-vinylpyrrolidone.

0461Suitable polyvinylpyrrolidones are, for example, commercial products such as Luviskol^® K 90 or Luviskol^® K 85 from BASF SE.

0462Suitable polyvinyl alcohols are, for example, under the trade names Elvanol^® by Du Pont or Vinol^® 523/540 distributed by Air Products.

0463Suitable polyvinyl acetate is, for example, under the trade name Vinac^® sold as an emulsion by Air Products.

0464Agents which as film-forming nonionic and / or setting nonionic polymer at least one polymer selected from the group that is formed from

0465Copolymer of maleic anhydride and methyl vinyl ether,

0466Polyvinyl pyrrolidone,

0467Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids with 2 to 18

0468Carbon atoms, in particular from N-vinylpyrrolidone and vinyl acetate,

0469Copolymers of N-vinylpyrrolidone and N-vinylimidazole and methacrylamide,

0470Copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,

0471Copolymers of N-vinylpyrrolidone with N, N-Di (Ci to C₄) Alkylamino (C₂ to C₄) - alkyl acrylamide,

0472Copolymers of N-vinylpyrrolidone with N, N-Di (Ci to C₄) Alkylamino (C₂ to C₄) - alkyl acrylamide,

0473or containing mixtures of these polymers are very particularly preferred according to the invention.

0474It is again preferred if the molar ratio of the structural units contained in the monomer N-vinylpyrrolidone to the structural units in the polymer comprised of the monomer vinyl acetate is in the range from 20 to 80 to 80 to 20, in particular from 30 to 70 to 60 to 40 .

0475Suitable copolymers of vinyl pyrrolidone and vinyl acetate are, for example, under the Luviskol trademark^® VA 37, Luviskol^® VA 55, Luviskol^® VA 64 and Luviskol^® VA 73 available from BASF SE. Further preferred powdery compositions according to the invention are characterized in that they contain as nonionic film-forming and / or nonionic setting polymer at least one copolymer (n1) which contains at least one structural unit according to formula (Ml) and at least one structural unit according to formula (M-Vll) and contains at least one structural unit according to formula (M-VIII)

0476<img file="WO2011069786A2_D0050.tif" />

0477It is also particularly preferred here if these copolymers, in addition to polymer units which result from the incorporation of the structural units mentioned according to formulas (M1-a), (I), (VII) and (VIII) into the copolymer, a maximum of 5% by weight, preferably contain at most 1% by weight of polymer units which are due to the incorporation of other monomers. The copolymers (n1) are preferably composed exclusively of structural units of the formulas (M1-a), (I), (VII) and (VIII) and can be represented by the general formula (Poly4)

0478<img file="WO2011069786A2_D0051.tif" />

0479describe, the indices m, n, o and p vary depending on the molecular weight of the polymer and should not mean that it is block copolymers. Rather, structural units of the formulas (I), (VII) and (VIII) can be statistically distributed in the molecule.

0480A particularly preferred polymer is selected from the polymers with the INCI name VP / methacrylamide / vinyl imidazole copolymer, which are available, for example, from BASF SE under the trade name Luviset Clear.

0481Also suitable according to the invention are those powdered compositions which contain at least one nonionic film-forming and / or nonionic setting polymer, comprising at least one structural unit of the formula (Ml) and at least one structural unit of the formula (M-III) <img file="WO2011069786A2_D0052.tif" />

0482wherein

0483R represents a hydrogen atom or a methyl group,

0484X¹ represents an oxygen atom or a group NH,

0485A represents a group of ethane-1,2-diyl, propane-1,3-diyl or butane-1,4-diyl

0486R² and R³ stand independently for one (Ci to C₄) Alkyl group.

0487It is particularly preferred if the above nonionic film-forming and / or nonionic setting polymer is selected from at least one polymer which fulfills at least one or more of the following features:

0488R represents a methyl group,

0489X¹ stands for a group NH,

0490A stands for ethane-1,2-diyl or propane-1,3-diyl,

0491R² and R³, independently of one another represent methyl or ethyl, (particularly preferably methyl).

0492The nonionic film-forming and / or nonionic setting polymer of this embodiment is particularly preferably at least one polymer which comprises at least one structural unit of the formula (Ml) and at least one structural unit of the formula (M-III-8),

0493<img file="WO2011069786A2_D0053.tif" />

0494A very particularly preferred nonionic film-forming and / or nonionic setting polymer of this embodiment is a copolymer of N-vinylpyrrolidone and N, N-dimethylaminiopropyl methacrylamide, which, for example, with the INCI name VP / DMAPA Acrylates Copolymer, for example under the trade name Styleze CC 10 from the company ISP is sold.

0495The agents according to the invention can furthermore contain the auxiliaries and additives which are usually added to conventional styling agents.

0496Additional care substances should be mentioned in particular as suitable auxiliaries and additives.

0497As a care substance, the agent can contain, for example, at least one protein hydrolyzate and / or one of its derivatives.

0498Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, the term protein hydrolyzates is also understood to mean total hydrolyzates and individual amino acids and their derivatives, as well as mixtures of different amino acids. Furthermore, according to the invention, polymers constructed from amino acids and amino acid derivatives are understood to be protein hydrolyzates. Of course, β-amino acids and their derivatives can also be used according to the invention. The molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

0499According to the invention, protein hydrolyzates of plant, animal, marine or synthetic origin can be used.

0500Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally be used in their place.

0501The protein hydrolyzates can be used in the agents according to the invention, for example in concentrations of 0.01% by weight to 20% by weight, preferably 0.05% by weight to 15% by weight and very particularly preferably in amounts of 0 , 05% by weight up to 5% by weight, based in each case on the entire application preparation.

0502As a care substance, the agent according to the invention can furthermore contain at least one vitamin, one provitamin, one vitamin precursor and / or one of their derivatives.

0503Vitamins, provitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred according to the invention.

0504The agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H. Panthenol, pantolactone, pyridoxine and its derivatives, and nicotinamide and biotin are particularly preferred. Like the addition of glycerol and / or propylene glycol, the addition of panthenol increases the flexibility of the polymer film formed when the agent according to the invention is used. If a particularly flexible hold is desired, the agents according to the invention can contain panthenol instead of or in addition to glycerol and / or propylene glycol. In a preferred embodiment, the agents according to the invention contain panthenol, preferably in an amount of 0.05 to 10% by weight, particularly preferably 0.1-5% by weight, in each case based on the total agent.

0505The agents according to the invention can furthermore contain at least one plant extract as a care substance. These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant. According to the invention, the extracts from green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, hake, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.

0506According to the invention, the plant extracts can be used both in pure and in diluted form. If they are used in dilute form, they usually contain about 2 to 80% by weight of active substance and, as a solvent, the extractant or mixture of extractants used in their extraction. Furthermore, it may be preferred to use mixtures of several, in particular two, different plant extracts in the agents according to the invention. The agents according to the invention preferably contain these care substances in amounts of 0.001 to 2, in particular from 0.01 to 0.5% by weight, in each case based on the entire application preparation.

0507By adding a UV filter, both the agent itself and the treated fibers can be protected against the harmful effects of UV radiation. At least one UV filter is therefore preferably added to the agent. The suitable UV filters are not subject to any general restrictions with regard to their structure and physical properties. Rather, all UV filters that can be used in the cosmetics sector are suitable, the absorption maximum of which lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (&lt;280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from approximately 280 to approximately 300 nm, are particularly preferred.

0508The UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters. Preferred UV filters are those whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.

0509The UV filters are usually contained in amounts of 0.01-5% by weight, based on the entire application preparation. Amounts of 0.1-2.5% by weight are preferred.

0510In a particular embodiment, the agent according to the invention further contains one or more substantive dyes. This enables the treated keratin fiber not only to be temporarily structured when using the agent, but also to be colored at the same time. This can be particularly desirable if only a temporary dyeing, for example with striking fashion colors, is desired, which can be removed from the keratinic fiber by simple washing.

0511Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those under the international names or Trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 1 1, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1 , HC Blue 2, HC Blue 1 1, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (ß-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- ( β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1 -Amino-4- (2'-hydroxyethyl) - amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2- nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4- Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

0512Cationic direct dyes are preferably used. Are particularly preferred

0513(a) cationic triphenylmethane dyes, such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

0514(b) aromatic systems which are substituted with a quaternary nitrogen group, such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, and

0515(c) direct dyes which contain a heterocycle which has at least one quaternary nitrogen atom, as are mentioned, for example, in EP-A2-998 908, to which reference is made explicitly here, in claims 6 to 11. Very particularly preferred cationic direct dyes of group (c) are the dyes known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51. The cationic direct dyes that are sold under the Arianor trademark^® are sold, are also very particularly preferred cationic direct dyes according to the invention.

0516The agents according to the invention according to this embodiment preferably contain the substantive dyes in an amount of 0.001 to 20% by weight, based on the total agent.

0517It is preferred according to the invention that the agents according to the invention are free from oxidation dye precursors. Oxidation dye precursors are divided into so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.

0518In addition to the components mentioned, the agents can furthermore contain all active ingredients, additives and auxiliaries known for such preparations.

0519Other active ingredients, auxiliaries and additives are, for example

0520Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite, fully synthetic hydrocolloids such as polyvinyl alcohol, and optionally crosslinked polyacrylates,

0521Structurants such as maleic acid and lactic acid,

0522Perfume oils, dimethyl isosorbide and cyclodextrins,

0523Defoamers like silicones,

0524Dyes for coloring the agent,

0525Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole,

0526Substances for adjusting the pH, such as customary acids, in particular

0527Edible acids, and bases,

0528Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers,

0529Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids,

0530Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbonates,

0531Hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

0532Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

0533Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,

0534Preservatives,

0535Antioxidants. With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art.

0536The agents according to the invention can be formulated in all the forms customary for styling agents, for example in the form of solutions which can be applied to the hair as a lotion or pump or aerosol spray, or other preparations which are suitable for use on the hair.

0537The agents according to the invention are preferably designed as a pump spray, aerosol spray, pump foam or aerosol foam. For this purpose, the agents according to the invention are assembled in a dispensing device, which is either a compressed gas container (“aerosol container”) additionally filled with a propellant or a non-aerosol container. The pressurized gas container, with the aid of which a product is distributed through the valve through the internal gas pressure of the container, is by definition called an "aerosol container". In reverse to the aerosol definition, a container under normal pressure is defined as a "non-aerosol container", with the aid of which a product is distributed by mechanical action through a pump or squeeze system.

0538The agents according to the invention are particularly preferably in the form of aerosol hair foam or aerosol hair spray. The agent according to the invention therefore preferably additionally contains at least one blowing agent.

0539Agents according to the invention, which are in the form of an aerosol product, can be produced in a customary manner. As a rule, all components of the agent according to the invention, with the exception of the propellant, are filled into a suitable pressure-resistant container. This is then closed with a valve. The desired amount of blowing agent is then introduced using conventional techniques.

0540In the embodiment as an aerosol spray, propellants suitable according to the invention are selected, for example, from N₂0, dimethyl ether, C0₂, Air, alkanes with 3 to 5 carbon atoms, such as propane, n-butane, iso-butane, n-pentane and iso-pentane, and mixtures thereof. Dimethyl ether, propane, n-butane, isobutane and mixtures thereof are preferred. According to a preferred embodiment, said alkanes, mixtures of said alkanes or mixtures of said alkanes with dimethyl ether are used as the only blowing agent. However, the invention also expressly includes the use of blowing agents of the chlorofluorocarbon type, but in particular the fluorocarbons. The propellant is preferably contained in the inventive agents of the embodiment as an aerosol spray in an amount of 30 to 60% by weight, based on the weight of the total agent.

0541Mixtures of propane and butane are very particularly preferably used as the sole blowing agent in a propane to butane weight ratio of from 20 to 80 to 15 to 85. These mixtures are in turn preferably used in the agents according to the invention in an amount of 30 to 55% by weight, based on the weight of the entire agent - used. According to the invention, butane is understood to mean n-butane, isobutane and mixtures of n-butane and isobutane.

0542With the given spray device, the sizes of the aerosol droplets and the respective size distribution can be adjusted via the ratio of amounts of propellant to the other components of the preparations.

0543The spray rate of the sprays according to the invention is preferably 6.5 to 10.0 g / 10 s.

0544Particularly preferred agents (aerosol sprays) according to the invention are packaged in an aerosol container with a star valve with a stem bore with a diameter of 0.27 to 0.35 mm. Such valves are sold, for example, as a KE or KEN type from Coster.

0545In the embodiment as an aerosol foam, propellants suitable according to the invention are selected, for example, from N₂0, dimethyl ether, C0₂, Air, alkanes with 3 to 5 carbon atoms, such as propane, n-butane, iso-butane, n-pentane and iso-pentane, and mixtures thereof. However, the invention also expressly includes the use of blowing agents of the chlorofluorocarbon type, but in particular the fluorocarbons. According to the embodiment of an aerosol foam, said alkanes, mixtures of said alkanes or mixtures of said alkanes with dimethyl ether are preferably used as the only blowing agent. Particularly preferred blowing agents are dimethyl ether, propane, n-butane, isobutane and mixtures thereof.

0546The size of the foam bubbles and the respective size distribution can be set for a given spray device via the ratio of amounts of blowing agent to the other constituents of the preparations.

0547When using conventional aerosol containers, aerosol foam products preferably contain the propellant in amounts of 1 to 35% by weight, based on the entire product. Amounts of 2 to 30% by weight, in particular 3 to 15% by weight, are particularly preferred. Isopentane is preferably suitable as a propellant for foaming gel-like agents in a two-chamber aerosol container, which is incorporated into the agents according to the invention and is assembled in the first chamber of the two-chamber aerosol container. In the second chamber of the two-chamber aerosol container, at least one other propellant, which is different from isopentane, is assembled, which builds up a higher pressure in the two-chamber aerosol container than the isopentane. The blowing agents of the second chamber are preferably selected from N₂0, dimethyl ether, C0₂, Air, alkanes with 3 or 4 carbon atoms (such as propane, n-butane, isobutane) and mixtures thereof.

0548The use of the additional preferred ingredients mentioned above and the amounts or ratios (vide supra) identified as preferred are of course also preferred in the context of all aerosol foam embodiment (s).

0549The agents and products according to the invention which contain the agents according to the invention, in particular aerosol hair sprays and aerosol hair foams, are distinguished in particular by the fact that they give treated hair a very natural shine and strong hold. A second subject of the invention is the use of an agent of the first subject of the invention for producing shine on fibers containing keratin, in particular human hair.

0550The products according to the invention, which contain these agents, in particular aerosol hair sprays, are distinguished in particular by the fact that they give treated hair a very strong, long-lasting hairstyle hold, although the hair remains flexible. A third subject of the invention is therefore the use of an agent of the first subject of the invention for the temporary deformation of keratin fibers, in particular human hair.

0551A fourth subject of the invention is a method for treating keratin-containing fibers, in particular human hair, in which, using a dispensing device, an agent according to the first subject of the invention is applied as a spray to the keratin-containing fibers.

0552It is preferred according to the invention that the keratin-containing fibers are shaped and this shape is fixed by the means of the first subject of the invention.

0553Furthermore, it is preferred if, after application of the agent according to the invention, the agent according to the invention remains from the keratin-containing fibers, ie is not rinsed out again.

0554The aforementioned delivery devices or aerosol products (vide supra) are considered preferred according to the invention. A fifth object of the invention is a method for the treatment of fibers containing keratin, in particular human hair, in which, using a dispensing device, an agent according to the first subject of the invention is foamed into a foam and the resulting foam is applied to the fibers containing keratin.

0555It is preferred according to the invention that the keratin-containing fibers are shaped and this shape is fixed by the means of the first subject of the invention.

0556Furthermore, it is preferred if, after application of the agent according to the invention, the agent according to the invention remains from the keratin-containing fibers, ie is not rinsed out again.

0557The aforementioned delivery devices (vide supra) are considered preferred according to the invention.

0558Examples

05591.0 Example I recipes

0560The following recipes were prepared by mixing the specified raw materials and filled into an aerosol can with a valve from Coster, type KE and a vortex nozzle from Coster "Standard micromist insert", type V06. The aerosol cans were closed with the valve and finally the appropriate blowing agents (here dimethyl ether) are added The following quantities are - unless stated otherwise - in percent by weight.

0561Table 1: Recipes &amp; comparative recipes

0562<img file="WO2011069786A2_D0054.tif" />

0563* Active substance on polymer

0564INCI name: Octylacrylamide / Acrylates / Butylaminoethyl Methacrylate Copolymer (National Starch)

0565² cross-linked copolymer of crotonic acid, vinyl (C₈ to Ci₂) -soalkyl esters and alpha, omega-vinyl dimethicone (acid number [mg KOH / g polymer]: 28-33) (Wacker Chemie AG)

0566³ cross-linked copolymer of crotonic acid, vinyl (C₈ to Ci₂) -soalkyl esters and alpha, omega-vinyl dimethicone (acid number [mg KOH / g polymer]: 63)

0567⁴ cross-linked copolymer of crotonic acid, vinyl (C₈ to C₁₂) -soalkyl esters and alpha, omega-vinyl dimethicone (acid number [mg KOH / g polymer]: 50

0568⁵ cross-linked copolymer of crotonic acid, vinyl (C₈ to Ci₂) -soalkyl esters and alpha, omega-vinyl dimethicone (acid number [mg KOH / g polymer]: 32)

0569After the application of the agents E1 to E4 to each strand of hair, these agents according to the invention brought about an excellent hairstyle hold. The hair got a natural shine and felt smooth. The comparative formulations V1 to V4 achieved poorer hair feel after application to each strand of hair, as well as lower gloss parameters or hairstyle holding parameters.

05702.0 Determine the hold

05712.1 Three-point bending test

0572The strands of hair (Kerling Internationale Haarfabrik GmbH, article number 826500 adhesive tress tight, type: European natural, color: 6/0, free hair length 130 mm, width 20 mm, weight 1.8 g, glued at one end) were glued at 1 ° to 50 ° C tempered water, containing 4 mL of a 25 wt .-% aqueous sodium laureth sulfate solution, and washed using ultrasound for 15 minutes. The tresses were rinsed thoroughly with lukewarm water and then combed. The water was carefully pressed out of the hair with the thumb and forefinger. This procedure was carried out three times per strand.

0573The strands of hair were hung on a frame at one end. A weight was attached to the other end of the strand of hair so that the hair was hanging straight down. The upper half and the lower half of a streak side were sprayed with one of the test hair sprays from a distance of 30 cm for a period of 10 seconds. The frame was rotated 180 ° and the opposite side of the previously sprayed side was also sprayed as previously described. The locks of hair were dried overnight at 296 K and a relative humidity of 50%. The strands were then carefully removed from the frame.

05745 strands of hair were prepared for each test hair spray and the maximum force applied until the polymer film broke was determined with the "Lloyd Intruments LF Plus" measuring device. At the start of the measurement, the load stamp of the measuring device was 40 mm from the test strand and was removed at a speed of 500 mm / minute towards the streak The mean values ​​of the measured values ​​were calculated and these were checked for statistical significance by means of Student's t-test. All values ​​were statistically significant. The results were as follows:

0575Table 2: Measurement results &amp; expected value

0576Hairspray (see Table 1) Fmax / N expected value F_Max / N difference to the expected value

V1 7.1 - -

V2 6.3 - -

V3 4.2 - -

0580V4 5.8 5.3 + 0.5

0581E4 6.7 5.7 + 1, 0 The degree of hold of the mixture E4 according to the invention is higher than the calculated expected value of the mixture. Furthermore, the degree of hold of E4 drops significantly less compared to the degree of hold of a mixture of amphomer and the crosslinked anionic copolymer (V4). The polymer combination according to the invention therefore achieves, in addition to excellent parameters with regard to gloss and hair feel, an optimally durable styling.