WO2012084400A2

WO2012084400A2 - Compositions for shaping keratinic fibres

Info

Publication number: WO2012084400A2
Application number: PCT/EP2011/070883
Authority: WO
Inventors: Burkhard Müller; Pamela Kaftan
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2010-12-23
Filing date: 2011-11-24
Publication date: 2012-06-28
Also published as: DE102010055814A1; WO2012084400A3

Abstract

The invention relates to cosmetic agents for temporarily shaping keratinic fibres, comprising in a cosmetic carrier a combination of i) at least one chitosan or a derivative thereof and ii) at least one cationic polymer, comprising, relative to the cationic polymer: at least 60.0 mol% of structural units of formula (M11), where R stands for a (C₁ to C₄) alkyl group, in particular a methyl group; and at least one structural unit of formula (M10), where n stands for 1 or 3. Said cosmetic agents produce styling with a high degree of hold, flexibility and conditioning.

Description

"Compositions for shaping keratinic fibers"

The present invention relates to cosmetic compositions for the temporary transformation of keratinic fibers, comprising in a cosmetic carrier a combination of at least one chitosan compound and at least one specific cationic polymer having imidazolinium residues.

An attractive-looking hairstyle is now generally considered an indispensable part of a well-groomed appearance. Due to current fashion trends, hairstyles are always considered to be chic, which in many types of hair only use firming

Build active ingredients or maintain for a longer period to several days. Therefore, hair treatment products that play a permanent or temporary

Shaping the hair serve an important role. Temporary shapes that should give a good hold, without affecting the healthy appearance of the hair, such as their gloss, can be achieved for example by hair sprays, hair waxes, hair gels, hair mousses, hair drier, etc.

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

The most important property of a composition for the temporary deformation of keratinic fibers, also referred to below as styling agent, is to give the treated fibers in the produced form the strongest possible hold. If the keratin fibers are human hair, it is also referred to as a strong hairstyle or the high degree of retention of the styling agent. The hairstyle hold is essentially determined by the type and amount of synthetic polymer used, but also an influence of the other components of the styling can be given by means of.

In addition to a high degree of hold, styling agents must meet a whole range of other requirements. These may be broad in properties on the hair, properties of the particular formulation, e.g. Properties of the foam, the gel or the sprayed aerosol, and properties that affect the handling of the styling agent, are subdivided, the properties of the hair have special significance. Particularly noteworthy are moisture resistance, low tackiness and a balanced conditioning effect.

In order to meet the different requirements, a large number of synthetic polymers has already been developed, which are used in styling agents. The polymers can be subdivided into cationic, anionic, nonionic and amphoteric fixing polymers. Ideally, the polymers when applied to the hair give one

Polymer film, on the one hand gives the hairstyle a strong grip, but on the other hand is sufficiently flexible so as not to break under stress. If the polymer film is too brittle, it results in the formation of so-called Filmpiaken, that is residues that detach during the movement of the hair and give the impression that the user of the corresponding styling agent would dandruff.

Object of the present invention was therefore to provide a means for temporary deformation ke ratin-containing fibers available, characterized by a high degree of hold

distinguished. Furthermore, the agent should simultaneously have a flexible hold and show a high care performance. The formation of Filmpiaken - in particular the formation of corresponding residues in the application, the brushing and drying of the keratin-containing fiber - should be avoided.

It has now surprisingly been found that this can be achieved by a combination of at least one chitosan (derivative) with a specific cationic polymer comprising at least 60.0 mol% Imidazoliniumstruktureinheiten.

A first subject of the invention is therefore a cosmetic composition for the temporary transformation of keratinic fibers, in particular human hair, containing in a cosmetic carrier i) at least one chitosan or its derivative and

ii) at least one cationic polymer comprising, based on the cationic polymer,

at least 60.0 mol% of structural units of the formula (M1 1)

"(M1 1)

wherein R is a (C 1 -C ₄ ) -alkyl group, in particular a methyl group, and - at least one structural unit of the formula (M 1 O)

(M10),

where n is 1 or 3.

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. According to the above formulas and all following formulas, a chemical bond marked with the symbol * stands for a free valency of the corresponding structural fragment.

Chitosans are biopolymers and are counted among the group of hydrocolloids. Chemically, these are partially deacetylated chitins of different molecular weight.

For the production of chitosans one starts from chitin, preferably the shell remnants of

Crustaceans, which are available as cheap raw materials in large quantities. The chitin is usually first deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights can be distributed over a broad spectrum. Preferably used are those having a weight average molecular weight of 800,000 to 1,200,000 daltons, a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation in the range of 80 to 88%, and have an ash content of less than 0.3 wt .-%.

In addition to the chitosans as typical biopolymers, cationically derivatized chitosans (such as, for example, quaternization products) or alkoxylated chitosans are also suitable as derivatives of chitosan for the purposes of the invention.

Agents preferred according to the invention are characterized in that they contain, as chitosan, at least one neutralization product of chitosan with at least one organic compound

Carboxylic acid, in particular formic acid, acetic acid, citric acid, lactic acid,

Pyrrolidonecarboxylic acid, tartaric acid, glycolic acid, nicotinic acid, hydroxyisobutyric acid,

Hydroxyisovaleric acid or mixtures of these acids. Here it is

According to the invention, preference is given to selecting the organic carboxylic acid from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid or mixtures of these acids. This neutralization product can be prepared, for example, in an aqueous medium by adding chitosan and the corresponding organic carboxylic acid.

Suitable chitosans are, for example, under the trade designations Hydagen ^® CMF (1 wt .-% of active substance in aqueous solution with 0.4 wt .-% of glycolic acid, molecular weight 500,000 to 5,000,000 g / mol Cognis), Hydagen ^® HCMF (chitosan (80% deacetylated), molecular weight of 50,000 to 1,000,000 g / mol, Cognis), Kytamer ^® PC (80 wt .-% of active substance of chitosan pyrolidoncarboxylat (INCI name: chitosan PCA), Amerchol) and Chitolam ^® NB / 101 freely available commercially.

The chitosans or their derivatives are preferably present in the compositions according to the invention in an amount of from 0.01% by weight to 5.0% by weight, particularly preferably from 0.05% by weight to 2.0% by weight. , very particularly preferably from 0.1 wt .-% to 1, 0 wt .-%, each based on the weight of the inventive composition. To compensate for the positive polymer charge of the cationic polymer ii) necessarily contained in the compositions of the invention are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

It is again preferred according to the invention if the cationic polymer ii) comprises at least one polymer which, in addition to at least 60 mol% of structural units of the formula (M1 1 -a), additionally comprises a structural element of the formula (M6)

To compensate for the positive polymer charge of these cationic polymers ii) in turn serve all possible physiologically acceptable anions, such as chloride, bromide,

Hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

Is to compensate the positive charge of the cationic polymer of the present invention ii) used a chloride ion, so this N-methylvinylimidazole are / vinylpyrrolidone copolymers are referred to as Polyquaternium-16, according to INCI nomenclature and are, for example, from BASF under the trade names Luviquat ^® Excellence available ,

It is particularly preferred if the cationic polymers ii) in addition to polymer units resulting from the incorporation of said structural units of the formula (M1 1) and (M6) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-% , contain additional structural units due to the incorporation of other monomers. The cationic polymers ii) are preferably composed exclusively of recurring units of the formulas (M1 1 -a) and (M6). The cationic polymers ii) can be used as additional structural units

Have structural units of the formula (M7)

Very particularly preferred cationic polymers ii), based in each case on the polymer, comprise 70.0 to 99.0 mol%, preferably 75.0 to 97.0 mol% and in particular 80.0 to 96.0 mol. -% structural units according to formula (M1 1) or formula (M1 1 -a). The cationic polymers ii) according to the invention are present in the agent according to the invention in a molecular weight distribution. The composition according to the invention preferably comprises cationic polymers ii) which have an average molecular weight M _{w of} from 1000 to 100 000 g / mol, more preferably from 3000 to 75000 g / mol, very particularly preferably from 5000 to 50 000 g / mol (in each case weight average). The molecular weight distribution was experimentally using

Gel filtration chromatography (column set: Novema 30, 1000 and 1000, each 8 x 300 mm and 10 μηι (PSS company), eluent: 0.5 M sodium nitrate / 10% (v / v) acetonitrile, detector: refractive index detector (Rl), sensitivity 64 , 30 ° C, eluent flow rate: 0.5 ml / min, injection volume: 100 μΙ_, column temperature: 30 ° C) against external calibration with dextran (dextran: "broard

Standards "with a molecular weight distribution of from 200 to 850000 g / mol from PSS.) The samples were prepared as follows: 4.0000 ± 0.3000 g of the said polymer (duplicate analysis) were weighed accurately into a precise volumetric 25 ml tube and the vessel filled to the mark with distilled water).

The said weight average is an average molecular weight which takes into account the total weight of the molecules of different molecular weight and not just the number of molecules. For the statistical calculation of the weight average, first the "weight fraction" w, = (Λ / i;) / [Z (/ Vi i)]

Are defined. This indicates the weight fraction of macromolecules in the sample from / ^'segments (z. B. monomer units) of the mass M exist and occur in the sample N-ma \. For the weight average molecular weight M _w = Zw, M, it is valid

M _w = [Z (/ Vi M ² i)] / [Z (/ Vi Mi)].

The said cationic polymers ii) are preferably present in the compositions according to the invention in an amount of from 0.01% by weight to 5.0% by weight, particularly preferably from 0.05% by weight to 2.0% by weight. , very particularly preferably from 0.1 wt .-% to 1, 0 wt .-%, each based on the weight of the inventive composition.

The following embodiments (A) to (F) are preferred according to the invention:

(A):

Cosmetic agent for the temporary transformation of keratinic fibers, in particular human hair, contained in a cosmetic carrier

i) 0.01 wt .-% to 5.0 wt .-%, particularly preferably from 0.05 wt .-% to 2.0 wt .-%, most preferably from 0.1 wt .-% to 1 , 0 wt .-%, each based on the weight of the inventive composition, at least one neutralization product of chitosan with at least one organic carboxylic acid and

ii) 0.01 wt .-% to 5.0 wt .-%, particularly preferably from 0.05 wt .-% to 2.0 wt .-%, most preferably from 0.1 wt .-% to 1 , 0% by weight (in each case based on the weight of the agent according to the invention) of at least one cationic polymer comprising at least 60.0 mol% (based on the cationic polymer) structural units of 1)

R "(M1 1)

(M10),

where n is 1 or 3, in particular 1.

(B):

i) 0.01 wt .-% to 5.0 wt .-%, particularly preferably from 0.05 wt .-% to 2.0 wt .-%, most preferably from 0, 1 wt .-% to 1 , 0 wt .-%, each based on the weight of the inventive composition, at least one at least one neutralization product of chitosan with at least one organic carboxylic acid and

ii) from 0.01% to 5.0%, more preferably from 0.05% to 2.0%, most preferably from 0.1% to 1% by weight , 0% by weight (in each case based on the weight of the agent according to the invention) of at least one cationic polymer comprising

at least 60.0 mol% (based on the cationic polymer) structural units of

1 )

R "(M1 1)

wherein R is a (C 1 to C ₄ ) -alkyl group, in particular a methyl group, and - at least one structural unit of the formula (M 1 O)

(M10), where n is 1 or 3, in particular 1.

(C):

i) at least one at least one neutralization product of chitosan with at least one organic carboxylic acid and

ii) at least one cationic polymer comprising, based on the cationic polymer,

From 70.0 to 99.0 mol%, preferably from 75.0 to 97.0 mol%, and in particular from 80.0 to 96.0, by weight of the formula (M1 1)

R "(M1 1)

wherein R is a (C 1 -C ₄ ) -alkyl group, in particular a methyl group, and - at least one structural unit of the formula (II)

where n is 1 or 3, in particular 1.

(D):

ii) at least one cationic polymer having a molecular weight M _w of 1000 to 100000 g / mol, preferably 3000 to 75000 g / mol, particularly preferably 5000 to 50 000 g / mol (in each case

Weight average) comprising, based on the cationic polymer,

at least 60 mol% of structural units of the formula (M1 1)

"(M1 1)

where n is 1 or 3, in particular 1.

(E):

Weight average) comprising, based on the cationic polymer,

From 70.0 to 99.0 mol%, preferably from 75.0 to 97.0 mol%, and in particular from 80.0 to 96.0, of the formula (M1 1)

R "(M1 1)

(M10),

where n is 1 or 3, in particular 1.

(F):

i) 0.01 wt .-% to 5.0 wt .-%, particularly preferably from 0.05 wt .-% to 2.0 wt .-%, most preferably from 0, 1 wt .-% to 1 , 0 wt .-%, each based on the weight of the inventive composition, at least one neutralization product of chitosan with at least one organic carboxylic acid and

ii) from 0.01% to 5.0%, more preferably from 0.05% to 2.0%, most preferably from 0.1% to 1% by weight , 0% by weight (in each case based on the weight of the agent according to the invention) of at least one cationic polymer comprising - 70.0 to 99.0 mol .-%, preferably 75.0 to 97.0 mol .-% and in particular 80.0 to 96.0 mol .-% of structural units of the formula (M1 1) (in each case based on the cationic polymer)

"(M1 1)

where n is 1 or 3, in particular 1.

(G):

ii) from 0.01% to 5.0%, more preferably from 0.05% to 2.0%, most preferably from 0.1% to 1% by weight , 0 wt .-%, (in each case based on the weight of the inventive composition) of at least one cationic polymer having a molecular weight M _w of 1,000 to 100,000 g / mol, preferably 3000 to 75000 g / mol, more preferably 5000 to 50,000 g / mol (each weight average), comprising

at least 60.0 mol% (based on the cationic polymer) structural units of

1 )

R "(M1 1)

where n is 1 or 3, in particular 1.

(H):

From 70.0 to 99.0 mol%, preferably from 75.0 to 97.0 mol% and in particular from 80.0 to 96.0 parts, based on the cationic polymer) structural units of the formula (M1 1)

R "(M1 1)

where n is 1 or 3, in particular 1.

The agents according to the invention contain their active ingredients in a cosmetic carrier, preferably in an aqueous cosmetic carrier, alcoholic cosmetic carrier or an aqueous-alcoholic cosmetic carrier. For the purpose of temporary hair remodeling, such carriers include, for example, lotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels, foams, pomades, waxes, or other preparations suitable for use are suitable on the hair. It is preferred according to the invention if it is a water-containing cosmetic carrier or an aqueous-alcoholic cosmetic carrier. It is inventively preferred if the cosmetic carrier of the inventive composition contains water, so that the inventive composition at least 50 wt .-% water - based on the weight of the total composition - contains.

For the purposes of the present invention, aqueous-alcoholic carriers are aqueous

Compositions containing 3 to 70 wt .-% of a C C ^ Alcohols, especially ethanol or isopropanol to understand. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol, 1, 2-propylene glycol or 1, 3-propylene glycol. Preference is given to all water-soluble organic solvents.

It is inventively preferred if the agent according to the invention additionally contains at least one film-forming and / or setting polymer. The additional film-forming and / or setting polymers of this embodiment of the agent according to the invention are different from the chitosan (derivatives) and the said cationic polymers ii). The film-forming and / or setting polymers may be nonionic, anionic, amphoteric or cationic, preferably nonionic or cationically charged.

According to the invention, polymers are understood as meaning compounds which are made up of a large number of molecules in which one or more types of atoms or

Atomic groupings (so-called constitutive units, basic building blocks or

Repeat units) are repeatedly lined up and have a molecular weight of at least 10,000 g / mol. The polymers are obtained by polyreaction, the latter being synthetic (i.e., synthetic) or natural.

Film-forming polymers are polymers which leave a continuous film on the skin, the hair or the nails when drying. 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. Particularly preferred are those polymers which have sufficient solubility in water, alcohol or water / alcohol mixtures. This makes it possible to produce appropriate solutions that can be applied or processed in a simple manner.

Film-forming polymers furthermore include those polymers which, when used in 0.01 to 20% strength by weight aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a transparent polymer film on the hair. Firming polymers contribute to the maintenance and / or build-up of the hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and therefore generally typical substances for shaping hair treatment agents such as hair setting agents,

Hair mousses, hair waxes, hair sprays. The film formation can be quite selective and connect only a few fibers.

The additional film-forming and / or setting polymers are preferably in an amount of 0.1 wt .-% to 10 wt .-%, in particular from 1, 0 wt .-% to 8.0 wt .-%, most preferably from 2.0 to 6.0 wt .-%, each based on the weight of the composition.

Within the scope of a particularly preferred embodiment, the compositions according to the invention contain as additional film-forming and / or setting polymer at least one film-forming nonionic and / or setting nonionic polymer.

The additional film-forming nonionic and / or setting nonionic polymers are preferably present in the composition according to the invention in an amount of from 0.1% by weight to 10.0% by weight, particularly preferably from 1.0% by weight to 8.0 Wt .-%, most preferably from 2.0 wt .-% to 6.0 wt .-%, each based on the weight of the inventive compositions.

Again, the film-forming nonionic and / or setting nonionic polymers are preferably selected from at least one polymer of the group that is formed

Homopolymers and nonionic copolymers of N-vinylpyrrolidone,

nonionic copolymers of isobutene,

nonionic copolymers of maleic anhydride.

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

Suitable polyvinyl acetate is marketed under the trade name Vinac ^® as an emulsion from Air Products.

Means comprising as film-forming nonionic and / or setting nonionic polymer at least one polymer selected from the group formed from

Copolymer of maleic anhydride and methyl vinyl ether,

polyvinylpyrrolidone,

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

Carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate,

or mixtures of these polymers are very particularly preferred according to the invention. In this case, those agents according to the invention which, as film-forming nonionic and / or consolidating nonionic polymer, are at least one polymer selected from the group which is formed, are in turn preferred polyvinylpyrrolidone,

Carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate,

or mixtures of these polymers.

When copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18

Carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate are used, it is again preferred if the molar ratio of the structural units contained in the monomer N-vinylpyrrolidone to the monomers from the vinyl esters of carboxylic acids having 2 to 18

Carbon atoms (especially vinyl acetate) contained structural units of the polymer in the range of 20 to 80 to 80 to 20, in particular from 30 to 70 to 60 to 40, is located.

Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example under the trademark Luviskol ^® VA 37, Luviskol ^® VA 55, Luviskol ^® VA 64 and Luviskol ^® VA 73 from the firm BASF SE.

The compositions according to the invention preferably comprise as additional film-forming and / or setting polymer at least one cationic, film-forming and / or cationic, fixing polymer. In this case, it is again preferred according to the invention if, as additional film-forming and / or setting polymer, at least one combination of

at least one nonionic, film-forming and / or nonionic, setting polymer and

at least one cationic, film-forming and / or cationic, fixing polymer is contained in the composition according to the invention.

Cationic polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic groups are quaternary ammonium groups. Especially such

Polymers in which the quaternary ammonium group is bonded via a C 1-4 -hydrocarboxylic group to a polymer main chain composed of acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

A cationic film-forming and / or cationic setting polymer which is preferably suitable according to the invention is at least one cationic film-forming and / or cationic setting polymer which contains at least one structural element of the formula (M9) and additionally at least one structural element of the formula (M10)

wherein

R is a hydrogen atom or a methyl group,

R ', R "and R" independently of one another represent a (C 1 to C ₃₀ ) -alkyl group,

X is an oxygen atom or a group NH,

A is an ethane-1,2-diyl group or a propane-1,3-diyl group,

n is 1 or 3.

Furthermore, at least one amphiphilic cationic polymer, at least one amphiphilic, cationic polymer comprising at least one structural unit of the formula (M6) and at least one structural unit of the formula (VI) and optionally at least one suitable as a preferred cationic film-forming and / or cationic fixing polymer

Structural unit of the formula (V)

wherein

R and R ⁴ independently of one another represent a hydrogen atom or a methyl group, A and A ² independently of one another represent a group of ethane-1,2-diyl, propane-1,3-diyl or butane-1,4-diyl,

R ² , R ³ , R ⁵ and R ⁶ independently of one another represent a (C 1 to C ₄ ) -alkyl group,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group.

It is inventively preferred if an inventive composition as the above suitable cationic film-forming and / or cationic setting polymer at least one amphiphilic, cationic polymer comprising at least one structural unit of the formula (M6), at least one structural unit of the formula (M7), at least one structural unit of Formula (II I) and at least one structural unit of the formula (IV),

R and R ⁴ independently of one another represent a hydrogen atom or a methyl group, X ¹ and X ² independently of one another represent an oxygen atom or a group NH,

A and A ² independently of one another are a group of ethane-1, 2-diyl, propane-1, 3-diyl or butane-1, 4-diyl,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group

contains.

To compensate for the positive polymer charge are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,

Tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

Such compounds are for example as

Copolymers of diethyl sulfate quaternized dimethylaminoethyl methacrylate, with

Vinylpyrrolidone having the INCI name Polyquaternium-1 1755, under the names Gafquat® 440, Gafquat ^® 734, Gafquat ^® (each ISP), and Luviquat PQ 1 1 PN (BASF SE),

Copolymers of N-vinylpyrrolidone, N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride (INCI name:

Polyquaternium-55), which, for example, under the trade name Styleze W 1 0 or W 20 (W 10: 1 0 wt .-% of active substance or W 20: 20 wt .-% active ingredient, each in ethanol-water mixture) of the Company ISP is distributed.

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

Furthermore, according to the invention, the cationic film-forming and / or cationic fixing polymers are particularly preferably selected from cationic, quaternized cellulose derivatives. Further suitable cationic and / or setting polymers are preferably cationic, quaternized cellulose derivatives.

Such cationic, quaternized celluloses prove to be particularly advantageous for the purposes of the invention, which carry more than one permanent cationic charge in a side chain. Among these cationic celluloses such cationic celluloses with the INCI name Polyquaternium-4 in turn, are particularly suitable, which are sold for example under the names of Celquat ^® H 100, Celquat L 200 ^® by the company National Starch.

Further particularly preferred agents according to the invention are characterized in that they contain as additional cationic film-forming and / or cationic setting polymer at least one copolymer (c1) which contains at least one structural unit of formula (M1 1 -a) and at least one structural unit of formula (M6) and at least one structural unit according to formula (M10) and at least one structural unit according to formula (M12)

(M12).

Here too, it is particularly preferred if the copolymers (c1) in addition to polymer units resulting from the incorporation of said structural units of the formula (M1 1 -a), (M6), (M8) and (M12) in the copolymer, a maximum of 5 wt .-%, preferably at most 1 wt .-%, contain polymer units, which go back to the incorporation of other monomers. Preferably, the

Copolymers (d) composed exclusively of structural units of the formula (M1 1 -a), (M6), (M8) and (M12).

To compensate for the positive polymer charge of the component (c1) are all possible physiologically acceptable anions, such as chloride, bromide, hydrogen sulfate,

Methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate or p-toluenesulfonate, triflate.

Wrd to compensate the positive charge of the polymer of formula (poly 3) a methosulfate be used refer to those N-methylvinylimidazole / vinylpyrrolidone / vinylimidazole / methacrylamide copolymers, according to INCI nomenclature as Polyquaternium-68 and are, for example, from BASF under the tradename Luviquat ^® Supreme available.

Other cationic polymers which can preferably be used in the agents according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic. Suitable temporary cationic polymers for the purposes of the invention are likewise those which have at least one structural unit of the formulas (M1-1) to (M1 -8)

,

In this case again those copolymers are preferred which contain at least one structural unit of the formulas (M1 -1) to (M1 -8) and additionally at least one structural unit of the formula (M10),

1 or 3 means.

Again, the group of polymers applies

Vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (for example, INCI name: Vinyl caprolactam / PVP / di-methylaminoethyl methacrylate copolymer (Gaffix ^® under the trade name VC 713 ISP)),

Vinylpyrrolidone / vinylcaprolactam / dimethylaminopropyl methacrylamide copolymer

(for example, INCI name: VP / vinyl caprolactam / DMAPA acrylates copolymer under the trade name Aquaflex ^® SF-40 (ISP)),

Vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (for example as a 35-39% solids in ethanol in the form of the commercial product Advantage LC E with the INCI name: vinyl caprolactam / VP / dimethylaminoethyl methacrylate copolymer, alcohol, lauryl pyrrolidone (ISP)), Vinylpyrrolidone / dimethylaminopropylmethacylamide copolymer (for example INCI name: VP / DMAPA Acrylates Copolymer under the trade name Styleze CC-10

(ISP)),

as a preferred list for selecting at least one or more polymers thereof.

It is particularly preferred according to the invention (very particularly preferably in connection with at least one of the preferred embodiments (A) to (H) (vide supra)), if the agents according to the invention are used as additional film-forming and / or setting polymer

(A) at least one amphiphilic, cationic polymer comprising at least one structural unit of the formula (M6), at least one structural unit of the formula (M7), at least one

Structural unit of the formula III) and at least one structural unit of the formula (IV),

wherein

R and R ⁴ independently of one another represent a hydrogen atom or a methyl group X ¹ and X ² independently of one another represent an oxygen atom or a group NH, A and A ² independently of one another represent a group of ethane-1,2-diyl, propane-1 , 3-diyl or butane-1, 4-diyl,

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group

and

(b) at least one amphiphilic, other than the amphiphilic cationic polymer,

cationic polymer comprising at least one structural unit of the formula (M6) and at least one structural unit of the formula (VI) and optionally at least one

Structural unit of the form

(VI) wherein

R ⁷ is a (C ₈ to C ₃₀ ) alkyl group.

and

(c) at least one film-forming nonionic and / or setting nonionic polymer, (in particular polyvinylpyrrolidone and / or a nonionic copolymer of N-vinylpyrrolidone and vinyl acetate).

Most preferably, the inventive composition additionally contains a

Polymer combinations of:

(a) copolymer of N-vinylpyrrolidone / N-vinylcaprolactam / N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride,

(b) terpolymer of N-vinylpyrrolidone, Ν, Ν-dimethylaminopropylmethacrylamide and N, N-dimethyl-N-dodecylammoniopropylmethacrylamide chloride,

(c) polyvinylpyrrolidone and / or nonionic copolymer of N-vinylpyrrolidone and vinyl acetate.

The above additional polymer combination contained in the agents according to the invention has the INCI designations:

(a) Polyquaternium-69 (b) Polyquaternium-55 (c) PVP and / or PVP / VA

The additional amphiphilic, cationic polymers (a) (vide supra) are preferably present in the composition in an amount, based on the total weight of the composition, of from 0.001% by weight to 2.0% by weight, particularly preferably 0.005% by weight .-% to 1, 0 wt .-%, most preferably from 0.01 to 0.5 wt .-%, included.

The additional amphiphilic, cationic polymers (b) (vide supra) according to the invention are preferably present in the composition in an amount of, based on the total weight of the composition, 0.01 wt .-% to 1, 5 wt .-%, particularly preferably from 0.05 wt .-% to 0.8 wt .-%, most preferably from 0.1 to 0.5 wt .-%, included.

Polyvinylpyrrolidone and / or nonionic copolymer of N-vinylpyrrolidone and vinyl acetate (c) are preferably present in the composition in an amount, based on the total weight of the composition, of from 0.1% to 10.0% by weight preferably from 0.5% to 8.0% by weight, most preferably from 1.0% to 5.0% by weight. Furthermore, such agents according to the invention are particularly suitable which additionally contain at least one (C 1 -C ₄ ) -hydroxyalkylcellulose, in particular hydroxyethylcellulose or hydroxypropylcellulose.

The (C 1 to C ₄ ) -hydroxyalkylcelluloses are preferably present in the agent according to the invention in an amount, based on the total weight of the agent, of from 0.1% by weight to 10.0% by weight, particularly preferably of 0, 5 wt .-% to 8.0 wt .-%, most preferably from 1, 0 to 5.0 wt .-%, included.

A particularly preferred cosmetic agent according to the invention comprises in a cosmetically acceptable carrier, based on the total weight of the agent,

i) 0.1 to 1.0% by weight of at least one chitosan or its derivative,

ii) from 0.1 to 1.0% by weight of at least one cationic polymer comprising, based on the cationic polymer,

- moles% of structural units of the formula (I)

R "(M1 1)

wherein R is a (C ^ to C ₄ ) alkyl group, in particular a

Methyl group, is, and

at least one structural unit of the formula (I)

where n is 1 or 3,

1.0 to 5.0% by weight of nonionic copolymer of N-vinylpyrrolidone and vinyl acetate, 0.1 to 0.5% by weight of terpolymer of N-vinylpyrrolidone, N, N-dimethylaminopropylmethacrylamide and N, N-dimethyl-N - dodecylammoniopropylmethacrylamide chloride

v) 0.01 to 0.5% by weight of at least one copolymer of N-vinylpyrrolidone / N-vinylcaprolactam / N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride, vi) 0.05 % to 0.5 wt .- (CT -C ₄₎ hydroxyalkyl. The embodiments of the features i) and ii) which have previously been found to be preferred according to the invention apply equally to this very particularly preferred embodiment of the invention.

It has proved to be preferable to additionally use at least one nonionic surfactant in the composition according to the invention. These surfactants can according to the invention already have emulsifying effect.

Nonionic surfactants contain as hydrophilic group e.g. a polyol group, one

Polyalkylene glycol ether group or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

Addition products of 2 to 100 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear or branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group , Addition products of 2 to 20 units of glycerol to linear or branched fatty alcohols having 8 to 30 carbon atoms in the alkyl group, to linear or branched fatty acids having 8 to 30 carbon atoms in the alkyl group, such as those among the

Sales names Dermofeel ^® G 10 LW (Straetman's Chemical Products) available types,

with a methyl or C ₂ - C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 1 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and with alkylphenols having 8 to 15 carbon -atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),

C ₂ -C ₃₀ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil, polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis),

alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula (E4-I) R CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I) in the R CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ² is hydrogen or methyl, R ^{3 is} linear or branched alkyl radicals having 1 to 4 carbon atoms and w is numbers from 1 to 20,

Amine oxides,

Hydroxymix ethers, as described for example in DE-OS 19738866, Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines,

Sugar surfactants of the alkyl and alkenyl oligoglycoside type of formula (E4-II),

R ⁴ 0- [G] _p (E4-II) in the R ⁴ for an alkyl or alkenyl radical having 4 to 22 carbon atoms, G for a

Sugar residue with 5 or 6 carbon atoms and p stands for numbers from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.

Of these, in turn, such nonionic surfactants are particularly preferably suitable for use in the composition according to the invention, which are selected from

Addition products of 2 to 20 units of glycerol to linear or branched fatty alcohols having 8 to 30 carbon atoms in the alkyl group,

Addition products of 2 to 20 units of glycerol to linear or branched fatty acids having 8 to 30 carbon atoms in the alkyl group,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil, mixtures of the aforementioned surfactants.

The nonionic surfactants are preferably in an amount of 0.005 wt .-% to 10 wt .-%, in particular from 0.01 to 2 wt .-%, each based on the weight of the inventive composition, in the inventive composition.

Furthermore, the inventive agent for increasing the hair care effect may additionally contain at least one cationic surfactant. However, a particularly good care effect is achieved by the agents according to the invention, so that an addition to a cationic surfactant to the agent according to the invention preferably does not take place. Examples of the cationic surfactants which can be used in the agents according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkyl methylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Furthermore, the very readily biodegradable quaternary ester compounds, so-called "esterquats", such as those marketed under the trademarks Dehyquart ^® and Stepantex ^® methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfate, can be used. The agents according to the invention are preferably present as foam. For this purpose, the agents according to the invention are packaged in a dispensing device which either represents an additional compressed gas container ("aerosol container") filled with a propellant or a non-aerosol container By definition, the term "non-aerosol container" is defined as a container under normal pressure, with the aid of which a product is distributed by mechanical action through a pumping or squeezing system.

With particular preference, the agents according to the invention are present as aerosol foam in one

Aerosol container before. The agent according to the invention therefore preferably additionally contains at least one propellant. In this context, in particular the embodiments (A) to (H) are considered to be preferably suitable, in an aerosol container with at least one propellant compound, compositions for providing an aerosol foam.

Compositions according to the invention, which are in the form of an aerosol product, can be prepared in a customary manner. In general, all constituents of the composition according to the invention, with the exception of the blowing agent, are introduced into a suitable pressure-resistant container. This is then closed with a valve. By conventional techniques, finally, the desired amount of blowing agent is introduced.

In the embodiment as an aerosol foam, blowing agents suitable according to the invention are selected, for example, from N ₂ O, dimethyl ether, CO ₂ , air, alkanes having 3 to 5

Carbon atoms such as propane, n-butane, iso-butane, n-pentane and iso-pentane, and their

Mixtures. According to the embodiment of an aerosol foam, said alkanes, mixtures of said alkanes or mixtures of said alkanes with dimethyl ether are used as sole blowing agent. However, the invention expressly also includes the concomitant use of propellants of the type of chlorofluorocarbons, but in particular of fluorocarbons.

Preference is given to dimethyl ether, propane, n-butane, isobutane and mixtures thereof. Very particular preference is given to using mixtures of propane and butane as the sole blowing agent in a weight ratio of propane to butane of from 70 to 30 to 15 to 85. These mixtures are again preferably present in the compositions according to the invention in an amount of from 3 to 15% by weight the weight of the entire agent - used. Under butane will

According to the invention, n-butane, isobutane and mixtures of n-butane and isobutane are understood.

About the ratio of blowing agent to the other constituents of the preparations can be at a given spray device, the sizes of the foam bubbles and the respective

Set size distribution. When conventional aerosol containers are used, aerosol foam products preferably contain the propellant in amounts of from 1 to 35% by weight, based on the total product. Amounts of 2 to 30 wt .-%, in particular from 3 to 15 wt .-% are particularly preferred.

For the foaming of gel-like agents in a two-chamber aerosol container isopentane is preferably suitable as a propellant, which is incorporated into the compositions according to the invention and is packaged in the first chamber of the two-chamber aerosol container. In the second chamber of the two-chamber aerosol container, at least one further propellant other than isopentane is made up, 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 N ₂ O, dimethyl ether, C0 ₂ , air, alkanes having 3 or 4 carbon atoms (such as propane, n-butane, iso-butane) and mixtures thereof.

A second subject of the invention is the use of a cosmetic agent of the first subject of the invention for the temporary reshaping and / or shape fixing of keratinous fibers, in particular human hair.

A third object of the invention is a method for the temporary transformation of keratinous fibers, in particular human hair, characterized in that a cosmetic agent of the first subject of the invention is applied to the keratinic fibers.

It has proved to be preferred if the keratinic fibers are not rinsed and left on the fiber after the action of the cosmetic compositions of the first subject of the invention.

The following examples are intended to illustrate the subject matter of the present invention without limiting it in any way.

B e i s p e e l e

The following formulation according to the invention was prepared in an aerosol container as aerosol foam product:

Chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000 g / mol, Cognis) copolymer of N-vinylpyrrolidone and vinyl acetate

3-Methyl-1-vinylimidazolium chloride-vinylpyrrolidone copolymer (95 mol% of 3-methyl-1-vinylimidazolium chloride to 5 mol% of N-vinylpyrrolidone) (M _w 25000, measured as described above)

Silicone glycol copolymer (INCI name: PEG-12 dimethicone) (Dow Corning)

The formulation E1 was applied to a subject for fixing the shape of the hairstyle as an aerosol foam. The hair received a natural shine, a strong hold of the hairstyle and a lasting volume.

Claims

Patent claims

1 . Cosmetic agent for the temporary transformation of keratinic fibers, in particular

human hair, containing in a cosmetic vehicle

i) at least one chitosan or its derivative and

ii) at least one cationic polymer comprising, based on the cationic polymer, at least 60.0 mol% of structural units of the formula (M1 1)

"(M1 1)

where n is 1 or 3.

2. Cosmetic composition according to claim 1, characterized in that the chitosan compound is at least one neutralization product of chitosan with at least one organic carboxylic acid.

3. Cosmetic composition according to claim 2, characterized in that the organic

Carboxylic acid is selected from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid or mixtures of these acids.

4. Cosmetic composition according to one of claims 1 to 3, characterized in that the chitosan compounds in an amount of 0.01 wt .-% to 5 wt .-%, preferably from 0.05 wt .-% to 2.0 wt .-%, more preferably from 0.1 wt .-% to 1 wt .-%, each based on the weight of the composition according to the invention are included.

5. Cosmetic agent according to one of claims 1 to 4, characterized in that

cationic polymer ii) at least one polymer is contained, in addition to at least 60 mol% of structural elements of the formula (M1 1 -a) additionally comprises at least one structural element of the formula (M6)

6. Cosmetic composition according to one of claims 1 to 5, characterized in that the cationic polymers ii) exclusively from repeating units of the formulas (M1 1) and (M6) (or (M1 1 -a) and (M6)) are constructed ,

7. Cosmetic composition according to one of claims 1 to 6, characterized in that the cationic polymers ii), in each case based on the cationic polymer, 70.0 to 99.0 mol .-%, preferably 75.0 to 97.0 mol .-% and in particular 80.0 to 96.0 mol .-% of structural units according to formula (M1 1) or formula (M1 1 -a) include.

8. Cosmetic composition according to one of claims 1 to 7, characterized in that the cationic polymers ii) an average molecular weight M _w of 1000 to 100000 g / mol, preferably 3000 to 75000 g / mol, particularly preferably 5000 to 50,000 g / mol (each

Weight average).

9. Cosmetic composition according to one of claims 1 to 8, characterized in that the cationic polymers ii) in an amount of 0.01 wt .-% to 5.0 wt .-%, preferably of 0.05 wt .-% to 2.0 wt .-%, particularly preferably from 0.1 wt .-% to 1, 0 wt .-%, each based on the weight of the composition according to the invention are included.

10. Cosmetic composition according to one of claims 1 to 9, characterized in that

additionally at least one film-forming nonionic and / or setting nonionic polymer is contained.

1 1. Cosmetic composition according to claim 10, characterized in that as a film-forming

nonionic and / or setting nonionic polymer at least one polymer selected from the group formed

polyvinylpyrrolidone,

Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, in particular N-vinylpyrrolidone and vinyl acetate,

or mixtures of these polymers is included.

Cosmetic composition according to one of claims 1 to 1 1, characterized in that in addition at least one film-forming cationic and / or setting cationic polymer is included.

13. Cosmetic composition according to one of claims 1 to 1 1, characterized in that it is at least one cationic film-forming and / or cationic setting polymer, the at least one structural element of the formula (M9) and as additional cationic film-forming and / or cationic setting polymer additionally at least one

Structure element of the formula (M10) contains

wherein

R is a hydrogen atom or a methyl group,

X is an oxygen atom or a group NH,

A is an ethane-1,2-diyl group or a propane-1,3-diyl group,

n is 1 or 3.

14. Cosmetic composition according to one of claims 1 to 13, characterized in that it comprises as additional film-forming and / or setting polymer at least one combination

at least one nonionic, film-forming and / or nonionic, setting polymer and

- contains at least one cationic, film-forming and / or cationic, fixing polymer.

15. Cosmetic composition according to one of claims 1 to 14, characterized in that it is present as a foam.