DE102009042727A1 - Hair cosmetic composition containing nitrocellulose-polyurethane-polyurea particles - Google Patents

Abstract

The present invention relates to hair cosmetic compositions containing nitrocellulose-polyurethane-polyurea particles.

Description

The present invention relates to the use of a composition containing nitrocellulose-polyurethane-polyurea particles as hair cosmetics. The hair cosmetic compositions are preferably poor in or free of volatile organic compounds (in the following: VOC-volatile organic compound).

To design and stabilize versatile hairstyles products are used, which are known as hair fixatives. The hair fixatives are mostly in the form of mousse or hair sprays. Mousse and hair sprays differ little in their composition but in their application. Mousse mousses are applied in damp hair as a tool to model the hairstyle. In contrast, spraying the hair sprays on dry ready-styled hair to fix the hairstyle. In addition to hair sprays and mousse also hair setting gels are offered.

In the case of hair sprays and mousses, the means for fixing or shaping the hairstyle are usually present as aerosol containers, squeeze bottles or by a pumping, spraying or frothing sprayable preparations consisting of an alcoholic or aqueous-alcoholic solution of film-forming natural or synthetic polymers consist. These polymers can be selected from the group of nonionic, cationic, amphoteric or anionic polymers. In the case of hair setting gels, the preparations described above are adjusted to an acceptable viscosity with conventional thickeners.

The film-forming polymers used are preferably anionic or amphoteric polymers based on acrylates. These polymers show a very good setting performance but the films formed are hard and brittle. This results in poor care services such as poor combability and an unpleasant feel.

When formulating cosmetic products, as in the case of technical applications, consideration must be given to reducing the proportion of propellants due to environmental regulations controlling the emission of volatile organic compounds into the atmosphere.

For the purposes of the present patent application under VOC organic, d. H. Carbon-containing substances understood that easily evaporate (are volatile) or already present as a gas at low temperatures (eg., At room temperature (23 ° C)). According to the invention, VOCs include in particular organic substances with boiling points in the range from -90 ° to 300 ° C., especially volatile hydrocarbons (eg propane, butane, i-butane, pentane, etc.), volatile ethers, such as dimethyl ether, volatile Alcohols such as methanol, ethanol, isopropanol and n-propanol and volatile amines. Above all, the proportion of VOC by amines and organic solvents such as alcohols should be reduced in the cosmetic formulations, for example by replacing alcohols with water.

Two solutions are conceivable for producing low-VOC formulations: dispersing the film-forming polymer in an aqueous system or dissolving the film-forming polymer in an aqueous-alcoholic system ( Aerosol and Spray Report, Vol. 37, n ° 3, 1998, 20-23 ). However, these solutions bring different problems. Thus, the use of aqueous polymer dispersions in a hair setting composition in use leads to a strong pearl effect, to peeling, to a long drying time or to a poor leachability. In the second proposed solution, the polymers are produced by neutralizing the carboxyl groups on the backbone with amines or alkalis. Although this allows the incorporation of the polymer and the formation of a low-VOC formulation, but at the expense of important properties, such as in particular curls in high humidity and drying time.

The use of polyurethanes in hair fixatives is known in principle. So describe the EP 1049446 A and the EP 1049443 A the use of a polyurethane in a hair care aerosol composition. However, the combability is not sufficient in the known compositions and also the feel is perceived as unpleasant.

The object of the present invention was to provide new hair cosmetic compositions, in particular hair setting compositions, which have very good combability, a pleasant feel, a good wash-off capability and a short drying time and at the same time are low in VOC or VOC-free.

Surprisingly, the object is achieved by the provision of hair cosmetic compositions, in particular hair-setting compositions comprising nitrocellulose-polyurethane-polyurea particles.

The invention therefore relates to the use of a composition containing nitrocellulose-polyurethane-polyurea particles as hair cosmetics.

The hair cosmetic compositions are generally water-containing, d. H. aqueous compositions in which the nitrocellulose-polyurethane-polyurea particles are dispersed, d. H. essentially unresolved. Water, optionally together with optional other liquid distribution media such as organic solvents such as ethanol, forms the major component (> 50% by weight) of the dispersing media based on the total amount of liquid dispersing media in the compositions. Optionally, water may also be the sole liquid dispersing medium.

The composition preferably has a volatile organic compound (VOC) content of less than 80% by weight, more preferably less than 55% by weight, even more preferably less than 40% by weight of the composition.

The aqueous dispersions of nitrocellulose polyurethane polyurea particles generally used to prepare the hair setting compositions preferably have a VOC of less than 10%, more preferably less than 3%, by weight more preferably less than 1% by weight, based on the aqueous dispersion of the nitrocellulose-polyurethane-polyurea particles.

The determination of the content of volatile organic compounds (VOC) is carried out in the context of the present invention, in particular by gas chromatographic analysis.

The nitrocellulose-polyurethane-polyurea particles which are present in the hair cosmetic formulations or in the aqueous dispersions of the nitrocellulose-polyurethane-polyurea particles used for the preparation of the hair cosmetic formulations preferably have an average particle size (average diameter) in the range from 20 to 700 nm measured by laser correlation spectroscopy (Dynamic Light Scattering on dilute aqueous dispersion with a Zetasizer 1000, Malvern Instruments, Malvern, UK). Preferably, the average particle size is between 50 and 500 nm, more preferably in the range between 100 and 400 nm.

und Harnstoff-Gruppen

als Wiederholungseinheiten aufweisen, wie sie insbesondere bei der Umsetzung der isocyanatterminierter Prepolymere A) mit aminofunktionellen Verbindungen B) gebildet werden. Bevorzugt weisen die Polyurethanpolyharnstoffe jeweils mindestens zwei der gezeigten Wiederholungseinheiten auf.Polyurethane polyureas according to the invention are polymeric compounds, the urethane groups:

and urea groups

have as repeat units, as they are formed in particular in the reaction of the isocyanate-terminated prepolymers A) with amino-functional compounds B). The polyurethane polyureas preferably each have at least two of the repeating units shown.

• A) Herstellung eines oder mehrerer isocyanatfunktioneller Prepolymere aus
• A1) einem oder mehreren organischen Polyisocyanaten
• A2) einem oder mehreren polymeren Polyolen mit zahlenmittleren Molekulargewichten von 400 bis 8000 g/mol, vorzugsweise 400 bis 6000 g/mol und besonders bevorzugt von 600 bis 3000 g/mol (hier und bei den folgenden Molekulargewichtangaben bestimmt durch Gelpermeationschromatographie gegenüber Polystyrol-Standard in Tetrahydrofuran bei 23°C), und OH-Funktionalitäten von 1,5 bis 6, bevorzugt 1,8 bis 3, besonders bevorzugt von 1,9 bis 2,1,
• A3) gegebenenfalls einer oder mehreren hydroxyfunktionellen Verbindungen mit Molekulargewichten von 62 bis 399 g/mol und
• A4) gegebenenfalls einem oder mehreren isocyanatreaktiven, anionischen, potentiell anionischen und/oder nichtionischen Hydrophilierungsmitteln,
• B) Umsetzen der freien NCO-Gruppen der Prepolymere aus Schritt A) mit einer oder mehreren aminofunktionellen Verbindungen unter Kettenverlängerung, welche bevorzugt ausgewählt werden aus
• B1) aminofunktionellen Verbindungen mit Molekulargewichten von 32 bis 399 g/mol und/oder
• B2) aminofunktionellen, anionischen oder potentiell anionischen Hydrophilierungsmitteln, wobei wahlweise ein oder mehrere organische Lösungsmittel vor der Kettenverlängerung in Schritt B), während der Kettenverlängerung in Schritt B) und/oder nach der Kettenverlängerung in Schritt B) zugesetzt werden,
• C) Dispergieren der Prepolymere aus Schritt A) oder der Umsetzungsprodukte mit aminofunktionellen Verbindungen aus Schritt B) in Wasser, wobei gegebenenfalls enthaltene potentiell ionische Gruppen durch teilweise oder vollständige Umsetzung mit einem Neutralisationsmittel in die ionische Form überführt werden können,
• D) Zugabe von Nitrocellulose in Form einer Lösung in einem organischen Lösemittel oder einem Lösemittelgemisch bevorzugt nach Schritt A) jedoch vor Schritt C), und
• E) Teilweises oder vollständiges destillatives Entfernen von organischem Lösemittel.

The polyurethane polyureas or the aqueous dispersions of the polyurethane polyureas or of the nitrocellulose polyurethane polyurea particles are preferably obtainable by a process comprising the following steps:

• A) Preparation of one or more isocyanate-functional prepolymers
• A1) one or more organic polyisocyanates
• A2) one or more polymeric polyols having number average molecular weights of 400 to 8000 g / mol, preferably 400 to 6000 g / mol and particularly preferably from 600 to 3000 g / mol (here and at the following molecular weight data determined by gel permeation chromatography over polystyrene standard in tetrahydrofuran at 23 ° C.), and OH functionalities of from 1.5 to 6, preferably from 1.8 to 3, particularly preferably from 1.9 to 2.1,
• A3) optionally one or more hydroxy-functional compounds having molecular weights of 62 to 399 g / mol and
• A4) optionally one or more isocyanate-reactive, anionic, potentially anionic and / or nonionic hydrophilicizing agents,
• B) reacting the free NCO groups of the prepolymers from step A) with one or more amino-functional compounds with chain extension, which are preferably selected from
• B1) amino-functional compounds having molecular weights of 32 to 399 g / mol and / or
• B2) amino-functional, anionic or potentially anionic hydrophilicizing agents, optionally adding one or more organic solvents before chain extension in step B), during chain extension in step B) and / or after chain extension in step B),
• C) dispersing the prepolymers from step A) or the reaction products with amino-functional compounds from step B) in water, optionally containing potentially ionic groups being converted into the ionic form by partial or complete reaction with a neutralizing agent,
• D) addition of nitrocellulose in the form of a solution in an organic solvent or a solvent mixture, preferably after step A) but before step C), and
• E) Partial or complete removal by distillation of organic solvents.

Preferred organic solvents for the preparation of the aqueous nitrocellulose-polyurethane-polyurea dispersions are aliphatic ketones, more preferably acetone or 2-butanone.

Suitable polyisocyanates of component A1) are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se to the person skilled in the art having an NCO functionality of ≥ 2.

Examples of such suitable polyisocyanates are 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4 ' -isocyanatocyclohexyl) methanes or mixtures thereof any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2 , 4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or 1,4-bis (2-isocyanato-prop-2-yl) -benzene (TMXDI), 1,3-bis ( isocyanato-methyl) benzene (XDI), (S) -alkyl 2,6-diisocyanatohexanoate, (L) -alkyl 2,6-diisocyanatohexanoate, with branched, cyclic or acyclic alkyl groups having up to 8 C atoms.

In addition to the polyisocyanates mentioned above, it is also possible proportionally to use modified diisocyanates having a uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and unmodified polyisocyanate having more than 2 NCO groups per molecule. B. 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4' '- are used with triisocyanate.

Preference is given to polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups and an average NCO functionality of the mixture of 2 to 4, preferably 2 to 2.6 and more preferably 2 to 2.4.

Hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof are particularly preferably used in A1).

In A2) are used polymeric polyols having a number average molecular weight M _n of 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and particularly preferably from 600 to 3000 g / mol. These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.

Such polymeric polyols are the polyester polyols known per se in polyurethane lacquer technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, and phenol / formaldehyde resins. These can be used in A2) individually or in any mixtures with each other.

As component A2) polyester polyols are preferred. Such polyester polyols are the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.

Examples of suitable diols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, neopentyl glycol and neopentyl glycol hydroxypivalate being preferred. In addition, it is also possible to use polyols, such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.

As dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2 Dimethyl succinic acid are used. The acid source used may also be the corresponding anhydrides.

If the mean functionality of the polyol to be esterified is greater than 2, monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid may additionally be used.

Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and, if appropriate, trimellitic acid.

Hydroxycarboxylic acids which can be co-used as reactants in the preparation of a hydroxyl-terminated polyester polyol include, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid, and the like. Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.

It is likewise possible in A2) to use hydroxyl-containing polycarbonates, preferably polycarbonatediols, having number-average molecular weights M _{n of} from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol. These are obtainable by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.

Examples of such diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, 3-methyl-1,5-pentanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A and lactone-modified diols of the aforementioned type in question.

Preferably, the diol component contains 40 to 100 wt .-% of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives. Such hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups. Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol.

Instead of or in addition to pure polycarbonate diols, it is also possible to use polyether-polycarbonate diols in A2).

Hydroxyl-containing polycarbonates are preferably of linear construction, but can also be obtained by the incorporation of polyfunctional components, in particular low molecular weight polyols, crosslinked. Glycerol, trimethylolpropane, hexanediol-1,2,6, butanetriol-1,2,4, trimethylolpropane, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or 1,3,4,6-dianhydrohexitols are suitable for this purpose, for example.

Likewise, in A2) polyether polyols can be used. Suitable examples are the polytetramethylene glycol polyethers known per se in polyurethane chemistry, such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.

Also suitable polyether polyols are the per se known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxides and / or epichlorohydrin to di- or polyfunctional starter molecules.

As suitable starter molecules, it is possible to use all compounds known from the prior art, for example water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.

As A2) polyester polyols, polytetramethylene glycol polyether polyols and / or polycarbonate polyols are preferably used. Especially preferred as component A2) are polyester polyols, most preferably polyester polyols based on adipic acid and hexanediol and neopentyl glycol (preferably having a mean molecular weight of from 1000 to 2500 g / mol).

In A3), polyols with molecular weights of 62 and 399 g / mol and with up to 20 carbon atoms can be used. These may be ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1 , 3-Butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A, (2,2-bis ( 4-hydroxycyclohexyl) propane), trimethylolpropane, glycerol, pentaerythritol and any mixtures thereof.

Also suitable are ester diols of the stated molecular weight range such as α-hydroxybutyl-ε-hydroxy-caproic acid ester, ω-hydroxyhexyl-γ-hydroxybutyric acid ester, adipic acid (β-hydroxyethyl) ester or terephthalic acid bis (β-hydroxyethyl) ester.

Furthermore, it is also possible to use monofunctional isocyanate-reactive hydroxyl-containing compounds in A3). Examples of such monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol mono-propyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1 -Hexadecanol.

In a preferred embodiment, the polyurethane polyurea used according to the invention contains less than about 10% by weight of component A3), preferably less than 5% by weight of component A3), based in each case on the total mass of the polyurethane polyurea, more preferably component A3) Preparation of polyurethane polyurea not used.

As component A4) one or more in particular isocyanate-reactive anionic, potentially anionic and / or nonionic hydrophilicizing agents are optionally used for the preparation of the polyurethanes used in the invention. The hydrophilicizing agents used as component A4) are in particular different from components A2) and A3).

Under anionic or potentially anionic hydrophilic compounds of component A4) are understood to mean all compounds which have at least one isocyanate-reactive hydroxyl group and at least one anionic or anionogenic (anion-forming) functionality, such. B.
-COOY, -SO ₃ Y, -PO (OY) ₂ (with Y, for example = H, NH ₄ ⁺ , metal cation, preferably alkali metal cation, in particular sodium cation), which undergo a pH-dependent dissociation equilibrium when interacting with aqueous media and thus can be negatively or neutrally charged. Suitable anionic or potentially anionic hydrophilizing compounds are in particular mono- and dihydroxycarboxylic acids, mono- and dihydroxysulfonic acids, and also mono- and dihydroxyphosphonic acids and their salts. Examples of such anionic or potentially anionic hydrophilicizing agents are dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid, and the adduct of sodium bisulfite with butene-2-diol-1,4, polyethersulfonate and the propoxylated adduct of 2-butenediol and NaHSO ₃ , as is in DE-A 2 446 440 , Page 5-9, formula I-III. Preferred anionic or potentially anionic hydrophilicizing agents of component A4) are those of the abovementioned type which have carboxy or carboxylate and / or sulfonate groups.

Particularly preferred anionic or potentially anionic hydrophilicizing agents are those which contain carboxyl and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of dimethylolpropionic acid or dimethylolbutyric acid.

Suitable nonionic hydrophilic compounds of component A4) are, for. As polyoxyalkylene ethers containing at least one hydroxy or amino group.

Examples are the monohydroxy-functional, preferably from 5 to 70, more preferably from 7 to 55, ethylene oxide units per molecule having polyalkylene oxide polyether alcohols, which are obtainable in a manner known per se by alkoxylation of suitable starter molecules (for example, in US Pat Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38 ).

These are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, preferably containing at least 30 mol%, more preferably at least 40 mol%, based on all the alkylene oxide units present of ethylene oxide units.

Particularly preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers having from 40 to 100 mole percent ethylene oxide and from 0 to 60 mole percent more preferably> 0 to 60 mole percent propylene oxide units.

Suitable starter molecules for such nonionic hydrophilicizing agents are saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-butanol. Tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as Phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as Morpholi n, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols of the abovementioned type. Particular preference is given to using diethylene glycol monobutyl ether or n-butanol as starter molecules.

Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.

Component B) is preferably selected from primary and / or secondary amines and / or diamines. It includes in particular diamines.

As component B) it is possible in particular to use amines which have no ionic or ionogenic, such as anionic hydrophilicizing groups (in the following component B1)), and it is possible to use amines which have ionic or ionogenic, in particular anionic hydrophilicizing groups ( in the following component B2)). In step B), the reaction of the prepolymer is preferably carried out by reacting a component B2), if appropriate in a mixture with component B1).

As component B1), for example, di- or polyamines such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, α, α, α ', α'-tetramethyl-1,3- and 1,4-xylylenediamine and 4,4-diaminodicyclohexylmethane and / or dimethylethylenediamine can be used. Also possible is the use of hydrazine or hydrazides such as adipic dihydrazide.

In addition, as component B1), it is also possible to use compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups. Examples of these are primary / secondary amines, such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-aminoethylethanolamine, ethanolamine , 3-aminopropanol, neopentanolamine.

Furthermore, as component B1), it is also possible to use monofunctional isocyanate-reactive amine compounds, for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine , Piperidine, or suitable substituted derivatives thereof, amide amines of diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary / tertiary amines such as N, N-dimethylaminopropylamine.

Most preferably, component B1) is 1,2-ethylene diamine.

Preferably, component B) comprises at least one component B2). By anionically or potentially anionically hydrophilicizing (di) amine compounds of component B2) are meant, for example, all compounds which contain at least one isocyanate-reactive amino group and at least one functionality, such as. B. -COOY, -SO ₃ Y, -PO (OY) ₂ (with Y, for example = H, NH ₄ ⁺ , metal cation, preferably alkali metal cation, in particular sodium cation) have. These groups undergo a pH-dependent dissociation equilibrium upon interaction with aqueous media and may thus be negatively or neutrally charged.

Suitable anionic or potentially anionic hydrophilizing compounds are mono- and diaminocarboxylic acids, mono- and diaminosulfonic acids and mono- and diaminophosphonic acids and their salts. Examples of such anionic or potentially anionic hydrophilicizing agents are N- (2-aminoethyl) -β-alanine, 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediaminepropyl or -butylsulfonic acid, 1,2- or 1,3-propylenediamine-β-ethylsulfonic acid , Glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid and the addition product of IPDI and acrylic acid ( EP-A 0 916 647 , Example 1), Furthermore, cyclohexylaminopropanesulfonic acid (CAPS) from WO-A 01/88006 be used as anionic or potentially anionic hydrophilicizing agent.

Preferred anionic or potentially anionic hydrophilicizing agents of component B2) are those of the abovementioned type which have carboxy or carboxylate and / or sulfonate groups.

Particularly preferred anionic or potentially anionic hydrophilicizing agents B2) are those which contain carboxylate and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-aminoethyl) -β-alanine, the 2- (2-amino -ethylamino) ethanesulfonic acid or the addition product of IPDI and acrylic acid ( EP-A 0 916 647 , Example 1). Most preferably, the diaminosulfonate is: NH ₂ -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -SO ₃ Na.

In a further preferred embodiment, a mixture of components B1) and B2) is used, in particular a mixture of 1,2-ethylenediamine and NH ₂ -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -SO ₃ -Na.

The aminic components B1) and / or B2) can optionally be used individually or in mixtures in water- or solvent-diluted form in the process according to the invention, wherein basically any order of addition is possible.

When water or organic solvents are used as the diluent, the diluent content in the chain-extending component used in B) is preferably 70 to 95% by weight.

The ratio of NCO groups of the compounds of component A1) to NCO-reactive groups such as amino, hydroxy or thiol groups of the compounds of components A2) to A4) is preferably 1.05 to 3 in the preparation of the NCO-functional prepolymer, 5, more preferably 1.2 to 3.0, particularly preferably 1.3 to 2.5.

The amino-functional compounds in step B) are used in such an amount that the equivalent ratio of isocyanate-reactive amino groups of these compounds to the free isocyanate groups of the prepolymer is preferably from 40 to 150%, more preferably from 50 to 125%, most preferably from 60 to 120%.

In a preferred embodiment, the components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
From 5 to 40% by weight of component A1),
From 55 to 90% by weight of component A2),
0 to 20 wt .-% of the components A3) and B1) and
0.1 to 25 wt .-% of components A4) and B2), wherein based on the total amounts of components A1) to A4) and B1) to B2) 0.1 to 5 wt .-% of anionic or potentially anionic hydrophilicizing agents A4) and B2) are used.

In a particularly preferred embodiment, the components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
From 5 to 35% by weight of component A1),
60 to 90% by weight of component A2),
0 to 15 wt .-% of the components A3) and B1) and
0.1 to 15 wt .-% of the components component A4) and B2), wherein based on the total amounts of components A1) to A4) and B1) to B2) 0.2 to 4 wt .-% of anionic or potentially anionic Hydrophilicizing agents A4) and B2) can be used.

In a very particularly preferred embodiment, the components A1) to A4) and B1) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
From 10 to 30% by weight of component A1),
65 to 85% by weight of component A2),
0 to 14 wt .-% of the components A3) and B1) and
0.1 to 13.5 wt .-% of components A4) and B2), wherein based on the total amounts of components A1) to A4) 0.5 to 3.0 wt .-% of anionic or potentially anionic hydrophilicizing agents are used ,

In step C), the prepolymers from step A) and / or the reaction products with amino-functional compounds from step 13) are dispersed in water, it being possible for any ionic groups which may be present to be converted into the ionic form by partial or complete reaction with a neutralizing agent. For partial or complete transfer of potentially anionic groups in anionic groups are useful bases such as tertiary amines, eg. B. trialkylamines having 1 to 12, preferably 1 to 6 carbon atoms in each alkyl or alkali metal bases such as the corresponding hydroxides used.

Examples of these are trimethylamine, triethylamine, methyldiethylamine, tripropylamine, N-methylmorpholine, methyldiisopropylamine, ethyldiisopropylamine and diisopropylethylamine. The alkyl radicals may, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol, alkyldialkanol and trialkanolamines. If appropriate, inorganic bases such as aqueous ammonia solution or sodium or potassium hydroxide can also be used as neutralizing agents.

Preference is given to ammonia, triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine and sodium hydroxide.

The molar amount of the bases is generally 50 and 125 mol%, preferably between 70 and 100 mol% of the molar amount of the acid groups to be neutralized. The neutralization can also take place simultaneously with the dispersion in which the dispersing water already contains the neutralizing agent.

The dispersion in water according to step C) is preferably carried out after the chain extension in step B).

For dispersion in water, the dissolved and chain-extended polyurethane polymer is optionally under high shear, such. By stirring vigorously, either in the dispersing water or, conversely, the dispersing water is stirred into the chain-extended polyurethane-polyurea polymer solutions. Preferably, the water is added to the dissolved chain-extended polyurethane polymer.

Suitable nitrocellulose in step D) is water-insoluble nitrocellulose of all nitrogen contents and viscosity stages. Nitrocelluloses which have, for example, the usual collodium qualities are preferred (for the term "collodium", see Römpp's Chemielexikon, Thieme Verlag, Stuttgart), d. H. Cellulose nitric acid esters, with a nitrogen content of 10 to 12.8 wt .-%, preferably a nitrogen content of 10.7 to 12.3 wt .-% based on dry matter of nitrocellulose.

Particularly preferred are cellulose nitric acid esters having a nitrogen content of 10.7 to 12.6 wt .-%, most preferably from 10.7 to 12.3 wt .-%. Examples of such are the Cellulosesalpetersäureester Walsroder® ^® nitrocellulose A types (Wolff Cellulosics GmbH & Co. KG, Bomlitz DE) ^® with a nitrogen content of 10.7 to 11.3 wt .-% or Walsroder® nitrocellulose AM-types (Wolff Cellulosics GmbH & Co. KG, Bomlitz DE) which have a nitrogen content of 11.3 to 11.8 wt .-% or Walsroder® ^® nitrocellulose e-types (Wolff Cellulosics GmbH & Co. KG, Bomlitz DE) with a nitrogen content of 11.8 to 12.3 wt .-%.

Within the aforementioned cellulose nitric acid esters of certain nitrogen contents, all viscosity stages are suitable in each case. Low-viscosity cellulose nitric acid esters of different nitrogen contents are correspondingly ISO 14446 divided into the following groups: ≥ 30 A, ≥ 30 M, ≥ 30 E. Medium-viscosity cellulose nitric acid esters of different nitrogen contents, according to ISO 14446 divided into the following groups: 18 E to 29 E, 18 M to 29 M, 18 A to 29 A. highly viscous cellulose nitric acid esters of different nitrogen contents, according to ISO 14446 are: ≤ 17 E, ≤ 17 M and ≤ 17 A.

It is also possible to use mixtures of different types of the abovementioned suitable cellulose nitric esters.

The nitrocellulose is usually supplied in a phlegmatized form in commercial form. Typical phlegmatizers are, for example, alcohols or water. The content of phlegmatizers is between 5 to 40 wt .-%. Nitrocelluloses which have been moistened with alcohols or water are preferably used to prepare the dispersions according to the invention. In a particularly preferred form, nitrocellulose moistened with 10 to 40% by weight of isopropanol (based on the total mass of the delivery form) is used. Examples include: "Walsroder ^® nitrocellulose E 560 isopropanol 30%" and "Walsroder ^® nitrocellulose A 500 isopropanol 30%."

The nitrocellulose is preferably added after step B) and before dispersion in water (step C)). For the addition, the nitrocellulose or phlegmatized nitrocellulose is expediently dissolved in an organic solvent or solvent mixture, more preferably dissolved in an aliphatic ketone and most preferably dissolved in acetone.

Finally, in step E) solvent contained in the dispersions is partially or completely separated by distillation.

The aqueous dispersion of nitrocellulose-polyurethane-polyurea particles used according to the invention preferably contains 1 to 50% by weight, particularly preferably 5 to 40% by weight and very particularly preferably 10 to 30% by weight of nitrocellulose.

The aqueous dispersion of nitrocellulose-polyurethane-polyurea particles used according to the invention preferably contains 1 to 50% by weight, more preferably 5 to 40% by weight and most preferably 10 to 30% by weight of polyurethane polyurea.

The weight ratio of polyurethane polyurea to nitrocellulose is preferably from (PUPH: NC) 1:10 to 10: 1, more preferably from 1: 3 to 4: 1, in the aqueous dispersion of the nitrocellulose-polyurethane-polyurea particles used according to the invention and in the hair cosmetic compositions of the invention. more preferably from 1: 2 to 3: 1.

The pH of the aqueous dispersions of nitrocellulose-polyurethane-polyurea particles used according to the invention is typically less than 9.0, preferably less than 8.5, more preferably less than 8.0.

The solids content of the aqueous dispersions of the nitrocellulose-polyurethane-polyurea particles used according to the invention, which are preferably used for the preparation of the hair cosmetic compositions of the invention, is generally from 10 to 70, preferably from 20 to 60, particularly preferably from 30 to 50,% by weight and completely particularly preferably from 35 to 45% by weight. The determination of the solids content is carried out according to DIN-EN ISO 3251 ,

The nitrocellulose-polyurethane-polyurea particles contained in the aqueous dispersions used according to the invention preferably have an average particle size (average diameter) of 20 to 700 nm, more preferably between 50 and 500 nm, even more preferably in the range between 100 and 400 nm, measured by means of laser Correlation Spectroscopy (Dynamic Light Scattering on Dilute Aqueous Dispersion with a Zetasizer 1000, Malvern Instruments, Malvern, UK).

In the aqueous dispersions used according to the invention, nitrocellulose-polyurethane-polyurea particles are present. It is a physical mixture of nitrocellulose and polyurethane polyurea.

The preparation of the hair cosmetic compositions of the invention generally takes place in such a way that the aqueous dispersions of the nitrocellulose-polyurethane-polyurea particles used according to the invention are mixed with at least one further hair-cosmetically active ingredient, which may optionally be present in a dissolving or dispersing medium.

In general, hair cosmetic compositions of the invention are compositions in which the nitrocellulose polyurethane polyurea particles are dispersed in a pharmaceutically acceptable distribution medium, preferably in an aqueous or aqueous organic distribution medium. In general, the hair cosmetic compositions contain at least about 5% by weight of water, preferably at least about 10% by weight of water, based on the total composition.

For the purposes of the present invention, the hair cosmetic compositions may advantageously be present as a mousse, liquid, hair spray, styling gels, styling cream, foam aerosol, emulsions or solutions.

The hair setting composition preferably contains from 0.1 to 20% by weight of the above-described nitrocellulose-polyurethane-polyurea particles, in particular from 0.5 to 15% by weight, based in each case on the total weight of the composition.

In addition to the polyurethane described above, the composition may contain further suitable film formers, which may in particular also contribute to the strengthening and styling of the hair.

The concentration of the further film formers can be from 0 to 20% by weight and in particular 0 to 10% by weight, based in each case on the total weight of the composition.

Advantageously, the film former (s) are selected from the group of water-soluble or water-dispersible polyurethanes used according to the invention, polyureas, silicone resins and / or polyesters and nonionic, anionic, amphoteric and / or cationic polymers and their mixtures.

• – Polyalkyloxazoline,
• – Vinylacetat Homo- oder Copolymerisate. Hierzu gehören beispielweise Copolymerisate aus Vinylacetat und Acrylsäureester, Copolymerisate aus Vinylacetat und Ethylen, Copolymerisate aus Vinylacetat und Maleinsäureester,
• – Acrylsäureester Copolymerisate wie z. B. die Copolymerisate aus Alkyl-Acrylat und Alkyl-Methacrylat, Copolymerisate aus Alkyl-Acrylat und Urethanen,
• – Copolymerisate aus Acrylnitril und nichtionischem monomer ausgewählt aus Butadien und (Meth)Acrylat,
• – Styrol Homo- und Copolymerisate. Hierzu gehören beispielweise Homopolystyrol, Copolymerisate aus Styrol und Alkyl-(Meth)Acrylat, Coplymerisate aus Styrol, Alkyl-Methacrylat und Alkyl-Acrylat, Copolymerisate aus Styrol und Butadien, Copolymerisate aus Styrol, Butadien und Vinylpyridin,
• – Polyamide,
• – Vinyllactame Homo- oder Copolymere, wie Vinylpyrrolidon-Homo- oder Copolymerisate; hierzu gehören beispielweise Polyvinylpyrrolidon, Polyvinylcaprolactam, Copolymerisate aus N-Vinylpyrrolidon und Vinylacetat und/oder Vinylpropionat in verschiedenen Konzentrationsverhältnissen, Polyvinylcaprolactam, Polyvinylamide und deren Salze sowie Copolymere aus Vinylpyrrolidon und Dimethylaminoethyl-methacrylat, Terpolymere aus Vinylcaprolactam, Vinylpyrrolidon und Dimethylaminoethylmethacrylat,
• – Polysiloxane,
• – Homopolymere des N-Vinylformamids z. B. PVF von National Starch.

Advantageous nonionic polymers, which may be present in compositions alone or in a mixture, preferably also with anionic and / or amphoteric and / or zwitterionic polymers, are selected from:

• Polyalkyloxazolines,
• - Vinyl acetate homo- or copolymers. These include, for example, copolymers of vinyl acetate and acrylic acid esters, copolymers of vinyl acetate and ethylene, copolymers of vinyl acetate and maleic acid esters,
• - Acrylic acid copolymers such. B. the copolymers of alkyl acrylate and alkyl methacrylate, copolymers of alkyl acrylate and urethanes,
• Copolymers of acrylonitrile and nonionic monomer selected from butadiene and (meth) acrylate,
• - Styrene homopolymers and copolymers. These include, for example, homopolystyrene, copolymers of styrene and alkyl (meth) acrylate, Coplymerisate of styrene, alkyl methacrylate and alkyl acrylate, copolymers of styrene and butadiene, copolymers of styrene, butadiene and vinylpyridine,
• - polyamides,
• - Vinyllactams homo- or copolymers, such as vinylpyrrolidone homo- or copolymers; these include, for example, polyvinylpyrrolidone, polyvinylcaprolactam, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate in various concentration ratios, polyvinylcaprolactam, polyvinylamides and their salts and copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, terpolymers of vinylcaprolactam, vinylpyrrolidone and dimethylaminoethyl methacrylate,
• - polysiloxanes,
• - Homopolymers of N-vinylformamide z. PVF from National Starch.

Particular preferred nonionic polymers are acrylic acid ester copolymers, homopolymers of vinylpyrrolidone and copolymers, polyvinylcaprolactam.

Very particular preferred nonionic polymers are homopolymers of vinylpyrrolidone z. B. Luviskol ^® K from BASF, copolymers of vinylpyrrolidone and vinyl acetate z. B. Luviskol ^® VA types of BASF or PVPVA ^® S630L the company ISP, terpolymers of vinylpyrrolidone, vinyl acetate and propionate such. B. Luviskol ^® VAP from BASF and Polyvinylcaprolactame z. B. Luviskol ^® PLUS from BASF.

Advantageous anionic polymers are homopolymers or copolymers with monomer units containing acid groups, which are optionally copolymerized with comonomers which contain no acid groups. Suitable monomers are unsaturated, free-radically polymerizable compounds which have at least one acid group, in particular carboxylic acid, sulfonic acid or phosphonic acid.

• – Acrylsäure oder Methacrylsäure Homo- oder Copolymer oder die Salze davon. Hierzu gehören beispielweise die Copolymerisate aus Acrylsäure und Acrylamide und/oder deren Natriumsalze, Copolymerisate aus Acrylsäure und/oder Methacrylsäure und einem ungesättigten Monomer ausgewählt aus Ethylene, Styrol, Vinylester, Acrylsäureester, Methacrylsäureester, gegebenenfalls ethoxylierten Verbindungen, Copolymerisate aus Vinylpyrrolidone, Acrylsäure und C1-C20 Alkyl Methacrylate z. B. Acrylidone^® LM der Firma ISP, Copolymerisate aus Methacrylsäure, Ethylacrylate und Tert-butyl Acrylate z. B. Luvimer^® 100 P der Firma BASF.
• – Crotonsäurederivat-Homo- oder Copolymer oder die Salze davon. Hierzu gehören beispielweise Vinylacetat/Crotonsäure-, Vinylacetat/Acrylat- und/oder Vinylacetat/Vinylneodecanoat/Crotonsäure-Copolymere, Natriumacrylat/Vinylalkohol-Copolymere,
• – ungesättigte C4-C8 Carbonsäurederivate oder Carbonsäureanhydrid Copolymer ausgewählt aus Copolymerisate aus Maleinsäure bzw. Maleinsäureanhydrid oder Fumarsäure bzw. Fumarsäureanhydrid oder Itaconsäure bzw. Itaconsäureanhydrid und mindestens einem Monomer ausgewählt aus Vinylester, Vinylether, Vinylhalogenderivate, Phenylvinylderivate, Acrylsäure, Acrylsäureester oder Copolymerisate aus Maleinsäure bzw. Maleinsäureanhydrid oder Fumarsäure bzw. Fumarsäureanhydrid oder Itaconsäure bzw. Itaconsäureanhydrid und mindestens einem Monomer ausgewählt aus Allylester, Methallylester und ggfs. Acrylamide, Methacrylamide, alpha-Olefin, Acrylsäureester, Methacrylsäureester, Vinylpyrrolidone. Weitere bevorzugte Polymere sind Methylvinylether/Maleinsäure-Copolymere, die durch Hydrolyse von Vinylether/Maleinsäureanhydrid-Copolymeren entstehen. Diese Polymere können auch teilverestert (Ethyl, Isopropyl- bzw. Butylester) oder teilamidiert sein.
• – in Wasser loesliche oder dispergierbare anionische Polyurethane, z. B. Luviset^®PUR von BASF, die von den erfindungsgemäßen Polyurethanen verschieden sind, wobei diese Aufstellung selbstverständlich nicht limitierend sein soll.

Advantageous anionic polymers containing carboxylic acid group are:

• - Acrylic acid or methacrylic acid homo- or copolymer or the salts thereof. These include, for example, the copolymers of acrylic acid and acrylamides and / or their sodium salts, copolymers of acrylic acid and / or methacrylic acid and an unsaturated monomer selected from ethylenes, styrene, vinyl esters, acrylates, methacrylates, optionally ethoxylated compounds, copolymers of vinylpyrrolidones, acrylic acid and C1- C20 alkyl methacrylates e.g. B. Acrylidone ^® LM from ISP, copolymers of methacrylic acid, ethyl acrylates and tert-butyl acrylates z. B. Luvimer ^® 100 P from BASF.
• - Crotonsäurederivat homo- or copolymer or the salts thereof. These include, for example, vinyl acetate / crotonic acid, vinyl acetate / acrylate and / or vinyl acetate / vinyl neodecanoate / crotonic acid copolymers, sodium acrylate / vinyl alcohol copolymers,
• Unsaturated C4-C8 carboxylic acid derivatives or carboxylic acid anhydride copolymer selected from copolymers of maleic acid or maleic anhydride or fumaric acid or fumaric acid or itaconic acid or itaconic anhydride and at least one monomer selected from vinyl esters, vinyl ethers, vinyl halide derivatives, phenylvinyl derivatives, acrylic acid, acrylic acid esters or copolymers of maleic acid or Maleic anhydride or fumaric acid or fumaric anhydride or itaconic acid or itaconic anhydride and at least one monomer selected from allyl ester, methallyl ester and, if appropriate, acrylamides, methacrylamides, alpha-olefin, acrylic esters, methacrylic acid esters, vinylpyrrolidones. Other preferred polymers are methyl vinyl ether / maleic acid copolymers formed by hydrolysis of vinyl ether / maleic anhydride copolymers. These polymers can also be partially esterified (ethyl, isopropyl or butyl ester) or partially amidated.
• - In water soluble or dispersible anionic polyurethanes, eg. B. Luviset ^® PUR BASF, which are different from the polyurethanes of the invention, this list is of course not intended to be limiting.

Advantageous anionic polymers containing sulfonic acid group are salts of polyvinyl sulfonic acid, salts of polystyrene sulfonic acid such as. For example, sodium polystyrene sulfonate or salts of polyacrylamide sulfonic acid.

Particularly advantageous anionic polymers are acrylic acid copolymers, crotonic acid derivative copolymer, copolymers of maleic acid or maleic anhydride or fumaric acid or fumaric acid or itaconic acid or itaconic anhydride and at least one monomer selected from vinyl esters, vinyl ethers, vinyl halide derivatives, phenylvinyl derivatives, acrylic acid, acrylic esters and salts of polystyrenesulphonic acid.

Very particular advantageous anionic polymers are acrylate copolymers, for. B. Luvimer of BASF, ethyl acrylate / N-tert-butylacrylamide / acrylic acid copolymers ULTRAHOLD ^® STRONG BASF, VA / crotonate / vinyl neodecanoate copolymer z. B. Resyn 28-2930 from National Starch, copolymers such. Z. Copolymers of methyl vinyl ether and maleic anhydride partially esterified z. B. Gantrez ^® the company ISP and sodium polystyrene sulfonates z. B. Flexan 130 from National Starch.

Advantageous amphoteric polymers may be selected from polymers containing randomly distributed units A and B in the polymer chain, wherein A represents a unit derived from a monomer having at least one basic nitrogen atom, and B is a unit derived from an acidic one Monomer having one or more carboxy groups or sulfonic acid groups, or A and B may represent groups derived from zwitterionic carboxybetaine monomers or sulfobetaine monomers; A and B may also mean a cationic polymer chain containing primary, secondary, tertiary or quaternary groups in which at least one amino group carries a carboxy group or sulfonic acid group which is bonded via a hydrocarbon group, or B and C are part of a polymer chain with ethylene-α β-dicarboxylic acid unit in which the carboxylic acid groups have been reacted with a polyamine containing one or more primary or secondary amino groups.

• – Polymere, die bei der Copolymerisation eines von einer Vinylverbindung mit Carboxygruppe abgeleiteten Monomers, wie insbesondere Acrylsäure, Methacrylsäure, Maleinsäure, α-Chloracrylsäure, und einem basischen Monomer gebildet werden, das von einer Vinylverbindung abgeleitet ist, die substituiert ist und mindestens ein basisches Atom enthält, wie insbesondere Dialkylaminoalkylmethacrylat und -acrylat, Dialkylaminoalkylmethacrylamid und -acrylamid. Solche Verbindungen sind in dem amerikanischen Patent Nr. 3 836 537 beschrieben worden.
• – Polymere mit Einheiten, die abgeleitet sind von: a) mindestens einem Monomer, das unter den Acrylamiden oder Methacrylamiden ausgewählt ist, die am Stickstoffatom mit einer Alkylgruppe substituiert sind, b) mindestens einem sauren Comonomer, das eine oder mehrere reaktive Carboxygruppen enthält, und c) mindestens einem basischen Comonomer, wie Estern von Acrylsäure und Methacrylsäure mit primären, sekundären, tertiären und quartären Aminosubstituenten und dem Quaternisierungsprodukt von Dimethylaminoethylmethacrylat mit Dimethylsulfat oder Diethylsulfat. Erfindungsgemäß besonders bevorzugte N-substituierte Acrylamide oder Methacrylamide sind Verbindungen, deren Alkylgruppen 2 bis 12 Kohlenstoffatome enthalten, besonders N-Ethylacrylamid, N-t-Butylacrylamid, N-t-Octylacrylamid, N-Octylacrylamid, N-Decylacrylamid, N-Dodecylacrylamid sowie die entsprechenden Methacrylamide. Die sauren Comonomere sind insbesondere unter Acrylsäure, Methacrylsäure, Crotonsäure, Itaconsäure, Maleinsäure, Fumarsäure sowie den Alkylmonoestern mit 1 bis 4 Kohlenstoffatomen von Maleinsäure, Maleinsäureanhydrid, Fumarsäure oder Fumarsäureanhydrid ausgewählt. Bevorzugte basische Comonomere sind Aminoethylmethacrylat, Butylaminoethylmethacrylat, N,N-Dimethylaminoethylmethacrylat, N-t-Butylaminoethylmethacrylat.
• – Vernetzte und ganz oder teilweise acylierte Polyaminoamide, die von Polyaminoamiden der folgenden allgemeinen Formel abgeleitet sind: -[CO-R-CO-Z]- worin R eine zweiwertige Gruppe bedeutet, die von einer gesättigten Dicarbonsäure, einer aliphatischen Mono- oder Dicarbonsäure mit ethylenischer Doppelbindung, einem Ester dieser Säuren mit einem niederen Alkanol mit 1 bis 6 Kohlenstoffatomen oder einer Gruppe abgeleitet ist, die bei der Addition einer dieser Säuren an ein bisprimäres oder bis-sekundäres Amin entsteht, und Z eine Gruppe bedeutet, die von einem bis-primären, mono- oder bis-sekundären Polyalkylenpolyamin abgeleitet ist, und vorzugsweise: a) in Mengenanteilen von 60 bis 100 Mol-% die Gruppen NH-[(CH₂)_x-NH-]_p- mit x = 2 und p = 2 oder 3 oder x = 3 und p = 2, wobei diese Gruppe, von Diethylentriamin, Triethylentetramin oder Dipropylentriamin abgeleitet ist; b) in Mengenanteilen von 0 bis 40 Mol-% die Gruppe -NH-[(CH₂)_x-NH-]_p-, worin x = 2 und p = 1, die von Ethylendiamin abgeleitet ist, oder die Gruppe, die von Piperazin stammt:
  
  c) in Mengenanteilen von 0 bis 20 Mol-%, die Gruppe -H-(CH₂)₆-NH-, die von Hexamethylendiamin abgeleitet ist, wobei diese Polyaminoamide durch Addition eines bifunktionellen Vernetzungsmittels, das unter den Epihalohydrinen, Diepoxiden, Dianhydriden und bis-ungesättigten Derivaten ausgewählt ist, in einer Menge von 0,025 bis 0,35 mol Vernetzungsmittel pro Aminogruppe des Polyaminoamids vernetzt und mit Acrylsäure, Chloressigsäure oder einem Alkansulton oder deren Salzen acyliert ist. Die gesättigten Carbonsäuren sind vorzugsweise unter den Säuren mit 6 bis 10 Kohlenstoffatomen ausgewählt, wie Adipinsäure, 2,2,4-Trimethyladipinsäure und 2,4,4,-Trimethyladipinsäure, Terephthalsäure; Säuren mit ethylenischer Doppelbindung, wie beispielsweise Acrylsäure, Methacrylsäure und Itaconsäure. Die bei der Acylierung verwendeten Alkansultone sind vorzugsweise Propansulton oder Butansulton, die Salze der Acylierungsmittel sind vorzugsweise die Natriumsalze oder Kaliumsalze.
• – Polymeren mit zwitterionischen Einheiten der folgenden Formel:
  
  worin R₁ eine polymerisierbare ungesättigte Gruppe bedeutet, wie Acrylat, Methacrylat, Acrylamid oder Methacrylamid, y und z ganze Zahlen von 1 bis 3 bedeuten, R₁₂ und R₁₃ ein Wasserstoffatom, Methyl, Ethyl oder Propyl bedeuten, R₁₄ und R₁₅ ein Wasserstoffatom oder eine Alkylgruppe bedeuten, die so gewählt ist, dass die Summe der Kohlenstoffatome R₁₄ und R₁₅ 10 nicht übersteigt. Polymere, die solche Einheiten enthalten, können auch Einheiten aufweisen, die von nicht zwitterionischen Monomeren stammen, wie Dimethyl- und Diethylaminoethylacrylat oder Dimethyl- und Diethylaminoethylmethacrylat oder Alkylacrylate oder Alkylmethacrylate, Acrylamide oder Methacrylamide oder Vinylacetat.
• – Polymere, die von Chitosan abgeleitet sind und Monomereinheiten enthalten, die den folgenden Formeln entsprechen:
  
  wobei die erste Einheit in Mengenanteilen von 0 bis 30%, die zweite Einheit in Mengenanteilen von 5 bis 50% und die dritte Einheit in Mengenanteilen von 30 bis 90% enthalten ist, mit der Maßgabe, dass in der dritten Einheit R₁₆ eine Gruppe der folgenden Formel bedeutet:
  
  worin bedeuten: falls q = 0, die Gruppen R₁₇, R₁₈ und R₁₉, die gleich oder verschieden sind, jeweils ein Wasserstoffatom, Methyl, Hydroxy, Acetoxy oder Amino, einen Monoalkylaminrest oder einen Dialkylaminrest, die gegebenenfalls durch ein oder mehrere Stickstoffatome unterbrochen und/oder gegebenenfalls mit einer oder mehreren Gruppen Amino, Hydroxy, Carboxy, Alkylthio, Sulfonsäure, Alkylthio, dessen Alkylgruppe einen Aminorest trägt, wobei mindestens eine der Gruppen R₁₇, R₁₈ und R₁₉ in diesem Fall ein Wasserstoffatom bedeutet; oder falls q = 1, die Gruppen R₁₇, R₁₈ und R₁₉ jeweils ein Wasserstoffatom, sowie die Salze, die diese Verbindungen mit Basen oder Säuren bilden.
• – Polymere, die der folgenden allgemeinen Formel entsprechen und die beispielsweise in dem französischen Patent 1 400 366 beschrieben sind:
  
  worin R₂₀ ein Wasserstoffatom, CH₃O, CH₃CH₂O oder Phenyl bedeutet, R₂₁ ein Wasserstoffatom oder eine niedere Alkylgruppe, wie Methyl oder Ethyl ist, R₂₂ ein Wasserstoffatom oder eine niedere C_1-6-Alkylgruppe bedeutet, wie Methyl oder Ethyl, R₂₃ eine niedere C_1-6-Alkylgruppe ist, wie Methyl oder Ethyl oder eine Gruppe der Formel: -R₂₄-N(R₂₂)₂, wobei R₂₄ eine Gruppe -CH₂-CH₂, -CH₂-CH₂-CH₂- oder -CH₂-CH(CH₃)- bedeutet und wobei R₂₂ die oben angegebenen Bedeutungen aufweist.
• – Polymere, die bei der N-Carboxyalkylierung von Chitosan gebildet werden können, wie N-Carboxymethylchitosan oder N-Carboxybutylchitosan.
• – Amphotere Polymere vom Typ -D-X-D-X, die ausgewählt sind unter: a) Polymere, die durch Einwirkung von Chloressigsäure oder Natriumchloracetat auf Verbindungen mit mindestens einer Einheit der folgenden Formel gebildet werden: worin D die Gruppe bedeutet
  
  und X die Symbole E oder E' bedeutet, wobei E oder E', die gleich oder verschieden sind, eine zweiwertige Gruppe bedeuten, bei der es sich um eine geradkettige oder verzweigte Alkylengruppe mit bis zu 7 Kohlenstoffatomen in der Hauptkette handelt, die unsubstituiert vorliegt oder mit Hydroxygruppen substituiert ist und ein oder mehrere Sauerstoffatome, Stickstoffatome oder Schwefelatome und 1 bis 3 aromatische und/oder heterocyclische Ringe enthalten kann; wobei die Sauerstoffatome, Stickstoffatome und Schwefelatome in Form der folgenden Gruppen vorliegen: Ether, Thioether, Sulfoxid, Sulfon, Sulfonium, Alkylamin, Alkenylamin, Hydroxy, Benzylamin, Aminoxid, quartäres Ammonium, Amid, Imid, Alkohol, Ester und/oder Urethan. b) Polymere der Formel worin D die Gruppe bedeutet
  
  und X das Symbol E oder E' und mindestens einmal E' bedeutet; wobei E die oben angegebenen Bedeutungen aufweist und E' eine zweiwertige Gruppe ist, bei der es sich um eine geradkettige oder verzweigte Alkylengruppe mit bis zu 7 Kohlenstoffatomen in der Hauptkette handelt, die unsubstituiert vorliegt oder mit einer oder mehreren Hydroxygruppen substituiert ist und ein oder mehrere Stickstoffatome enthält, wobei das Stickstoffatom mit einer Alkylgruppe substituiert ist, die gegebenenfalls durch ein Sauerstoffatom unterbrochen ist und zwingend eine oder mehrere Carboxyfunktionen oder eine oder mehrere Hydroxyfunktionen enthält und durch Umsetzung mit Chloressigsäure oder Natriumchloracetat betainisiert ist.
• – Alkyl(C_1-5)vinylether/Maleinsäureanhydrid-Copolymere, die teilweise durch Semiamidierung mit einem N,N-Dialkylaminoalkylamin wie N,N-Dimethylaminopropylamin oder einem N,N-Dialkylaminoalkohol teilweise modifiziert sind. Diese Polymere können auch weitere Comonomere enthalten, wie Vinylcaprolactam.
• Ganz besondere vorteilhafte amphotere Polymere sind z. B. die Copolymere Octylacrylamid/Acrylate/Butylamino-Ethylmethacrylat-Copolymer, die unter den Bezeichnungen AMPHOMER^®, AMPHOMER^® LV 71 oder BALANCE^® 47 der Firma NATIONAL STARCH im Handel sind, und Methylmethacrylat/Methyl-dimethylcarboxymethylammoniumethylmethacrylat-Copolymere.

Particular advantageous amphoteric polymers are:

• Polymers formed in the copolymerization of a monomer derived from a vinyl compound having a carboxy group, such as, in particular, acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a basic monomer derived from a vinyl compound which is substituted and at least one basic atom contains, in particular dialkylaminoalkyl methacrylate and acrylate, Dialkylaminoalkylmethacrylamid and -acrylamide. Such compounds are in the U.S. Patent No. 3,836,537 been described.
• Polymers having units derived from: a) at least one monomer selected from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group, b) at least one acid comonomer containing one or more reactive carboxy groups, and c) at least one basic comonomer, such as esters of acrylic acid and methacrylic acid with primary, secondary, tertiary and quaternary amino substituents and the quaternization product of dimethylaminoethyl methacrylate with dimethyl sulfate or diethyl sulfate. N-substituted acrylamides or methacrylamides which are particularly preferred according to the invention are compounds whose alkyl groups contain 2 to 12 carbon atoms, especially N-ethylacrylamide, Nt-butylacrylamide, Nt-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acidic comonomers are selected in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the alkyl monoesters having 1 to 4 carbon atoms of maleic acid, maleic anhydride, fumaric acid or fumaric anhydride. Preferred basic comonomers are aminoethyl methacrylate, butylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, Nt-butylaminoethyl methacrylate.
• Crosslinked and completely or partially acylated polyaminoamides derived from polyaminoamides of the following general formula: - [CO-R-CO-Z] - wherein R is a divalent group derived from a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid having ethylenic double bond, an ester of these acids with a lower alkanol having 1 to 6 carbon atoms or a group which in the addition of one of these acids a bis-primary or bis-secondary amine is formed, and Z is a group derived from a bis-primary, mono- or bis-secondary polyalkylenepolyamine, and preferably: a) in proportions of 60 to 100 mol%, the groups NH-- [(CH ₂ ) _x -NH-] _p - where x = 2 and p = 2 or 3 or x = 3 and p = 2, which group is derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine; b) in proportions of 0 to 40 mol% of the group -NH - [(CH ₂ ) _x -NH-] _p -, wherein x = 2 and p = 1, which is derived from ethylenediamine, or the group derived from Piperazine comes from:
  
  c) in proportions of 0 to 20 mol%, the group -H- (CH ₂ ) ₆ -NH-, which is derived from hexamethylenediamine, said polyaminoamides by addition of a bifunctional crosslinking agent among epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives is crosslinked in an amount of 0.025 to 0.35 mol of crosslinking agent per amino group of the polyaminoamide and is acylated with acrylic acid, chloroacetic acid or an alkanesultone or salts thereof. The saturated carboxylic acids are preferably selected from acids having 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyl adipic acid and 2,4,4-trimethyl adipic acid, terephthalic acid; Ethylenic double bond acids such as acrylic acid, methacrylic acid and itaconic acid. The alkanesultones used in the acylation are preferably propanesultone or butanesultone, the salts of the acylating agents are preferably the sodium salts or potassium salts.
• - Polymers with zwitterionic units of the following formula:
  
  wherein R _{1 is} a polymerizable unsaturated group, such as acrylate, methacrylate, acrylamide or methacrylamide, y and z are integers from 1 to 3, R ₁₂ and R _{13 is} a hydrogen atom, methyl, ethyl or propyl, R ₁₄ and R _{15 denote} a hydrogen atom or an alkyl group chosen such that the sum of the carbon atoms R ₁₄ and R ₁₅ does not exceed 10. Polymers containing such moieties may also contain moieties derived from non-zwitterionic monomers such as dimethyl and diethylaminoethyl acrylate or dimethyl and diethylaminoethyl methacrylate or alkyl acrylates or alkyl methacrylates, acrylamides or methacrylamides or vinyl acetate.
• Polymers derived from chitosan containing monomeric units corresponding to the following formulas:
  
  wherein the first unit is contained in proportions of 0 to 30%, the second unit in proportions of 5 to 50% and the third unit in proportions of 30 to 90%, with the proviso that in the third unit R _{16 is} a group of following formula means:
  
  wherein: if q = 0, the groups R ₁₇ , R ₁₈ and R ₁₉ , which are identical or different, each represent a hydrogen atom, methyl, hydroxy, acetoxy or amino, a monoalkylamine radical or a dialkylamine radical optionally substituted by one or more nitrogen atoms interrupted and / or optionally with one or more groups amino, hydroxy, carboxy, alkylthio, sulfonic acid, alkylthio, the alkyl group carries an amino radical, wherein at least one of the groups R ₁₇ , R ₁₈ and R ₁₉ in this case represents a hydrogen atom; or if q = 1, the groups R ₁₇ , R ₁₈ and R _{19 are} each a hydrogen atom, as well as the salts which form these compounds with bases or acids.
• Polymers which correspond to the following general formula and which are described, for example, in US Pat French Patent 1 400 366 are described:
  
  wherein R _{20 represents} a hydrogen atom, CH ₃ O, CH ₃ CH ₂ O or phenyl, R _{21 represents} a hydrogen atom or a lower alkyl group such as methyl or ethyl, R _{22 represents} a hydrogen atom or a lower C _1-6 alkyl group such as Methyl or ethyl, R _{23 is} a lower C _1-6 alkyl group, such as methyl or ethyl, or a group of the formula: -R ₂₄ -N (R ₂₂ ) ₂ , where R _{24 is} a group -CH ₂ -CH ₂ , - CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH (CH ₃ ) - and wherein R _{22 has} the meanings given above.
• Polymers which can be formed in the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan.
• - DXDX-type amphoteric polymers selected from: (a) polymers formed by the action of chloroacetic acid or sodium chloroacetate on compounds containing at least one unit of the formula: in which D represents the group
  
  and X represents the symbols E or E ', wherein E or E', which are the same or different, represent a divalent group which is a straight-chained or branched alkylene group having up to 7 carbon atoms in the main chain which is unsubstituted or substituted with hydroxy groups and may contain one or more oxygen atoms, nitrogen atoms or sulfur atoms and 1 to 3 aromatic and / or heterocyclic rings; wherein the oxygen atoms, nitrogen atoms and sulfur atoms are in the form of the following groups: ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxy, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane. b) Polymers of the formula wherein D is the group
  
  and X is the symbol E or E 'and at least once E'; wherein E has the meanings given above and E 'is a divalent group which is a straight-chain or branched alkylene group having up to 7 carbon atoms in the main chain which is unsubstituted or substituted by one or more hydroxy groups and one or more Contains nitrogen atoms, wherein the nitrogen atom is substituted with an alkyl group which is optionally interrupted by an oxygen atom and necessarily contains one or more carboxy or one or more hydroxy functions and betainisiert by reaction with chloroacetic acid or sodium chloroacetate.
• Alkyl (C _1-5 ) vinyl ether / maleic anhydride copolymers partially partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or an N, N-dialkylaminoalcohol. These polymers may also contain other comonomers, such as vinyl caprolactam.
• Very particular advantageous amphoteric polymers are, for. For example, the copolymers octylacrylamide / acrylates / butylamino-ethyl methacrylate copolymer, which are under the designations AMPHOMER ^® , AMPHOMER ^® LV 71 or BALANCE ^® 47 from NATIONAL STARCH commercially, and methyl methacrylate / methyl-dimethylcarboxymethylammoniumethylmethacrylat copolymers.

It may be advantageous to neutralize the anionic and amphoteric polymers with suitable bases to improve their water solubility or water dispersibility.

As neutralizing agents for polymers containing acid groups, the following bases can be used: hydroxides whose cation is an ammonium or an alkali metal such as. As NaOH or KOH.

Other neutralizing agents are primary, secondary or tertiary amines, amino alcohols or ammonia. Preference is given here to 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol (AEPD), 2-amino-2-methyl-1-propanol (AMP ), 2-amino-1-butanol (AB), 2-amino-1,3-propanediol, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine ( TIPA), dimethyl laurylamine (DML), dimethyl myristalamine (DMM), and dimethyl stearamine (DMS).

Neutralization may be partial or complete depending on the application.

Optionally usable but less preferred are cationic polymers such as polymers containing primary, secondary tertiary and / or quaternary amino groups which are part of the polymer chain or directly attached to the polymer chain.

The cosmetically acceptable medium, which generally forms part of the hair cosmetic composition according to the invention, contains in particular water and optionally a cosmetically suitable solvent. The preferred solvents are C 2-4 aliphatic alcohols such as ethanol, isopropanol, t-butanol, n-butanol; Polyol such as propylene glycol, glycerin, ethylene glycol and polyol ethers; Acetone; unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane; and their mixtures selected.

Very particular preferred solvent is ethanol.

However, the content of such solvents is in accordance with the fact that according to the invention are preferably low in VOC hair fixative compositions, preferably less than 80 wt .-%, more preferably less than 55 wt .-%, more preferably less as 40% by weight.

The proportion of water may in particular be in the range, for example, from 10 to 94% by weight, preferably from 20 to 80% by weight, more preferably from more than 30 to 70% by weight, based on the total weight of the composition. The medium is advantageously also an aqueous-alcoholic mixture. The proportion of the alcohol in the mixture is in the range of 0 to 90 wt .-%, preferably 0 to 70 wt .-%, more preferably 0 to 55 wt .-%, more preferably from 0 to 40 wt .-%, based on the total weight the composition.

• – Vernetzte oder nichtvernetzte Acrylsäure oder Methacrylsäure Homo- oder Copolymere. Hierzu gehören vernetzte Hompolymere von Methacrylsäure oder Acrylsäure, Copolymerisate aus Acrylsäure und/oder Methacrylsäure und Monomeren, die von anderen Acryl- oder Vinylmonomeren abgeleitet sind, wie C10-30 Alkylacrylate, C10-30-Alkylmethacrylate und Vinylacetat.
• – Verdickende Polymere natürlicher Herkunft beispielweise auf Cellulosebasis, Guargummi, Xanthan, Scleroglucan, Gellangummi, Rhamsan und Karayagummi, Alginate, Maltodextrin, Stärke und ihre Derivate, Johannisbrotkernmehl, Hyaluronsäure.
• – Nichtionische, anionische, kationische oder amphotere assoziative Polymere z. B. auf Basis von Polyethylenglycole und ihre Derivate, oder Polyurethane.
• – Vernetzte oder nichtvernetzte Homopolymere oder Copolymere auf Basis von Acrylamid oder Methacrylamid, wie Homopolymere von 2-Acrylamido-2-methylpropansulfonsäure, Copolymere von Acrylamid oder Methacrylamid und Methacryloyloxyethyltrimethylammoniumchlorid oder Copolymere von Acrylamid und 2-Acrylamido-2-methylpropansulfonsäure angegeben werden.

The hair fixatives may furthermore advantageously contain thickeners. Advantageous thickeners are:

• - Crosslinked or non-crosslinked acrylic acid or methacrylic acid homo- or copolymers. These include crosslinked homopolymers of methacrylic acid or acrylic acid, copolymers of acrylic acid and / or methacrylic acid and monomers derived from other acrylic or vinyl monomers, such as C10-30 alkyl acrylates, C10-30 alkyl methacrylates and vinyl acetate.
• - Thickening polymers of natural origin, for example, based on cellulose, guar gum, xanthan, scleroglucan, gellan gum, rhamsan and karaya gum, alginates, maltodextrin, starch and its derivatives, locust bean gum, hyaluronic acid.
• Nonionic, anionic, cationic or amphoteric associative polymers e.g. B. based on polyethylene glycols and their derivatives, or polyurethanes.
• Crosslinked or non-crosslinked homopolymers or copolymers based on acrylamide or methacrylamide, such as homopolymers of 2-acrylamido-2-methylpropanesulfonic acid, copolymers of acrylamide or methacrylamide and methacryloyloxyethyltrimethylammonium chloride or copolymers of acrylamide and 2-acrylamido-2-methylpropanesulfonic acid.

Particularly advantageous thickeners are thickening polymers of natural origin, crosslinked acrylic acid or methacrylic acid homo- or copolymers and crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid.

Very particularly advantageous thickeners are xanthan gum, such as the products supplied under the names Keltrol ^® and Kelza ^® by CP Kelco or the products from RHODIA with the Name Rhodopol and guar gum, such as those sold under the name Jaguar ^® HP105 by the company Rhodia.

Very particularly advantageous thickeners are crosslinked homopolymers of methacrylic acid or acrylic acid, from Lubrizol under the names Carbopol ^® 940, Carbopol ^® 941, Carbopol ^® 980, Carbopol ^® 981, Carbopol ^® ETD 2001, Carbopol ^® EDT 2050, Carbopol ^® 2984 Carbopol ^® 5984, and Carbopol ^® Ultrez 10 ^® from 3V under the names Synthalen K, Synthalen ^® L and Synthalen ^® MS and PROTEX under the names Modarez ^® V 1250 PX, Modarez ^® V2000 PX, Viscaron ^® A1600 PE and Viscaron ^® A700 PE are commercially available.

Very particular advantageous thickeners are crosslinked copolymers of acrylic acid or methacrylic acid and a C _10-30 -alkyl acrylate or C _10-30 -alkyl methacrylate and copolymers of acrylic acid or methacrylic acid and vinylpyrrolidone. Such copolymers are, for example, from Lubrizol under the names Carbopol ^® 1342, Carbopol ^® 1382, Pemulen ^® TR1 or Perulen ^® TR2 and from ISP under the names Ultrathix P-100 (INCI: Acrylic Acid / VP Crosspolymer) commercially available ,

Very particular advantageous thickeners are crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid. Such copolymers are, for example, by the company Clariant under the names Aristoflex ^® AVC: available (INCI ammonium acryloyldimethyltaurate / VP Copolymer)

If used, the thickeners are generally present at a level of from 0% to 2% by weight, preferably from 0% to 1% by weight, based on the total weight of the composition.

The hair fixatives may further contain a propellant gas. It is advantageous to use the propellant in an amount of 0 to 40% by weight and more preferably in a concentration of 0 to 20% by weight based on the total weight of the formulation.

The preferred propellants of the invention are hydrocarbons such as propane, isobutane and n-butane and mixtures thereof. But also compressed air, carbon dioxide, nitrogen, nitrogen dioxide and dimethyl ether and mixtures of all these gases are advantageous to use according to the invention.

Of course, the person skilled in the art knows that there are per se nontoxic propellants which would in principle be suitable for the realization of the present invention in the form of aerosol preparations, but which should nevertheless be dispensed with because of a harmful effect on the environment or other concomitant circumstances, in particular fluorohydrocarbons and chlorofluorocarbons (US Pat. CFCs) such as. B. 1,2-difluoroethane (propellant 152 A).

Hair-setting active ingredients can furthermore be used in the hair setting formulations. As care substances may preferably cyclic polydimethylsiloxanes (cyclomethicones) in concentrations of z. B. 0-1.0 wt .-% of the total formulation or silicone surfactants (polyether-modified siloxanes) of the type dimethicone copolyol or simethicone z. B. in concentrations 0-1,0 wt .-% of the total weight of the composition are preferably used. Cyclomethicones are, inter alia, under the trade names Abil ^® K4 from Goldschmidt or z. DC 244, DC 245 or DC 345 from Dow Corning. Dimethicone copolyols are z. B. under the trade name DC 193 from Dow Corning and Belsil ^® DM 6031 from Wacker offered.

Optionally, conventional additives may also be included in the hair setting composition, for example to impart certain modifying properties to the composition: these are silicones or silicone derivatives, wetting agents, humectants, plasticizers such as glycerin, glycol and phthalates and ethers, fragrances and perfumes, UV absorbers , Dyes, pigments, and other colorants, anticorrosives, neutralizers, antioxidants, detackifiers, combiners and conditioners, antistatic agents, brighteners, preservatives, proteins and derivatives thereof, amino acids, vitamins, emulsifiers, surfactants, viscosity modifiers, thickeners and rheology modifiers, gelling agents , Opacifiers, stabilizers, surfactants, sequestering agents, chelating agents, pearlescing agents, aesthetic enhancers, fatty acids, fatty alcohols, triglycerides, botanical extracts, clarifying aids and film formers.

These additives are generally present at a level of from about 0.001% to 15% by weight, preferably from 0.01% to 10% by weight, based on the total weight of the hair setting composition.

The hair fixative compositions may advantageously be in a pump spray or aerosol package. The hair setting compositions according to the invention can advantageously be foamed with a propellant gas. Accordingly, pump spray, aerosol packaging, and foam pump or aerosol package based foam dispensers containing the hair setting composition of the invention are also part of the invention.

A preferred embodiment of the hair setting compositions is in the form of a spray which additionally contains one or more of the following constituents: cosmetically suitable solvents, such as aliphatic alcohols having 2-4 carbon atoms, preferably ethanol, polyols, acetone, unbranched or branched hydrocarbons, cyclic hydrocarbons and mixtures thereof, and propellants such as hydrocarbons, compressed air, carbon dioxide, nitrogen, nitrogen dioxide, dimethyl ether, fluorocarbons and chlorofluorocarbons, preferably dimethyl ether and / or a propane / butane mixture.

The present invention will be illustrated by the following examples. All amounts, proportions and percentages are, unless stated otherwise, based on the weight and the total amount or on the total weight of the compositions.

Examples

Substances used and abbreviations:

• Diaminosulphonate (diaminosodium sulphonate): NH ₂ -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -SO ₃ Na (45% in water)
• Desmophen ^® C2200: polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)

The nitrocellulose types used in each case were obtained from Dow Wolff Cellulosics GmbH & Co. KG, Walsrode, Germany.

Unless otherwise noted, all percentages are by weight.

Unless otherwise noted, all analytical measurements were carried out at 23 ° C.

The determination of the solids content was carried out according to DIN-EN ISO 3251 ,

NCO contents were volumetrically determined unless expressly stated otherwise DIN EN ISO 11909 certainly.

The mean particle sizes of the dispersions were determined by means of laser correlation spectroscopy measurements (Zetasizer 1000, Malvern Instruments, Malvern, UK).

Example 1:

Preparation of 60% WALSRODER NITROCELLULOSE E560 (stabilized with 30% water), modified aqueous polyurethane dispersion (ester-based), hereinafter referred to as NC-PUD1:

131.8 g of a difunctional polyester polyol based on adipic acid and hexanediol and neopentyl glycol (average molecular weight 1700 g / mol, OH = about 66 mg KOH / g of substance) was heated to 65.degree. Subsequently, 23.3 g of hexamethylene diisocyanate were added at 65 ° C within 5 min and stirred at 100 ° C until the theoretical NCO value of 3.3% was reached. The finished prepolymer was dissolved with 275.7 g of acetone at 50 ° C and then added a solution of 4.1 g Diaminosatriumsulfonat 6.1 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 354 g WALSRODER NITROCELLULOSE E560 / 30% water and 1547 g acetone was added within 5 min. The dispersion was carried out by adding 560 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 40.9% and an average particle size of 353 nm.

Example 2:

Preparation of 50% WALSRODER NITROCELLULOSE E560 (stabilized with 30% water), modified aqueous polyurethane dispersion (ester-based), hereinafter referred to as NC-PUD 2:

131.8 g of a difunctional polyester polyol based on adipic acid and hexanediol and neopentyl glycol (average molecular weight 1700 g / mol, OH = about 66 mg KOH / g of substance) was heated to 65.degree. Subsequently, 23.3 g of hexamethylene diisocyanate were added at 65 ° C within 5 min and stirred at 100 ° C until the theoretical NCO value of 3.3% was reached. The finished prepolymer was dissolved with 275.7 g of acetone at 50 ° C and then added a solution of 4.1 g Diaminosatriumsulfonat 6.1 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 236 g WALSRODER NITROCELLULOSE E560 / 30% water and 1031 g acetone was added within 5 min. The dispersion was carried out by adding 560 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 41.2% and an average particle size of 251 nm.

Example 3:

Preparation of 40% WALSRODER NITROCELLULOSE E560 (stabilized with 30% water), modified aqueous polyurethane dispersion (ester-based), hereinafter referred to as NC-PUD 3:

131.8 g of a difunctional polyester polyol based on adipic acid and hexanediol and neopentyl glycol (average molecular weight 1700 g / mol, OH = about 66 mg KOH / g of substance) was heated to 65.degree. Subsequently, 23.3 g of hexamethylene diisocyanate were added at 65 ° C within 5 min and stirred at 100 ° C until the theoretical NCO value of 3.3% was reached. The finished prepolymer was dissolved with 275.7 g of acetone at 50 ° C and then added a solution of 2.4 g Diaminosatriumsulfonat, 1.4 g of ethylenediamine and 3.6 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 154.7 g WALSRODER NITROCELLULOSE E560 / 30% water and 675 g acetone was added within 5 min. The dispersion was carried out by adding 560.5 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 40.3% and an average particle size of 176 nm.

Example 4:

Preparation of 30% WALSRODER NITROCELLULOSE E560 (stabilized with 30% water), modified aqueous polyurethane dispersion (ester-based), hereinafter referred to as NC-PUD 4:

131.8 g of a difunctional polyester polyol based on adipic acid and hexanediol and neopentyl glycol (average molecular weight 1700 g / mol, OH = about 66 mg KOH / g of substance) was heated to 65.degree. Subsequently, 23.3 g of hexamethylene diisocyanate were added at 65 ° C within 5 min and stirred at 100 ° C until the theoretical NCO value of 3.3% was reached. The finished prepolymer was dissolved with 275.7 g of acetone at 50 ° C and then added a solution of 2.84 g Diaminosatriumsulfonat, 0.96 g of ethylenediamine and 4.26 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 100 g WALSRODER NITROCELLULOSE E560 / 30% water and 437 g acetone was added within 5 min. The dispersion was carried out by adding 560.5 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 41.0% and an average particle size of 283 nm.

Application Comparative Experiments:

For the Kämmkraftmessung be commercial European mixed hair Kerling (useful length: 19 cm, Kerling color number 6/0). The hair is subjected to a standardized washing procedure before use. The hair soaked in water for 15 minutes is shampooed with 15% by weight sodium dodecylsulfate solution for two minutes, rinsed thoroughly with warm water, cold-dry-bled and conditioned at 22 ° C. and 55% relative humidity. 0.5 cm wide strands of hair become damp on spiral winder wrapped, blended dry for 35 minutes, then sprayed with hair cosmetics composition and conditioned overnight.

The combing force is measured automatically (combing machine, DWI, Aachen). Three combs drive alternately through the bundled strand and a sensor records the acting force. Before the start of the test, a standardized manual combing is carried out 15 times. Each individual strand is combed a total of 75 times, and each run is done on five strands.

The comb force change is measured before and after treatment with the hair cosmetics composition.

For the measurement, a formulation with 50% by weight of volatile organic compounds was prepared, each containing 2% by weight of the polymers shown in Table 1 (based on solids of the polymer relative to the total weight of the formulation).

For the application of the VOC 50 formulation the spray head of the company Seaquist Perfect Dispensing GmbH is used: pump sprayer type PZ1 / 150 HV 24/410). From a distance of 30 cm, the formulations are applied to the hair material by rapid actuation of the spray head.

The results are shown in Table 1: TABLE 1 Influence of the hair setting composition on the comb force (the lower the value, the better the combability): Combination force change (%) formulations 6 sprays 12 sprays Polyurethane A (comparison) 49 ± 5 57 ± 7 Polyurethane B (comparison) 71 ± 5 Polyurethane Polyurea / Nitrocellulose C (Invention) 36 ± 4 40 ± 5 Acrylate Polymer (comparative) 54 ± 8
A polyurethane: Polyurethane of the prior art, Luviset PUR from BASF ^®, INCI name: Polyurethane-1, Polyurethane from a diisocyanate, dimethylol propionic acid, polyester diol and aliphatic diol.
Polyurethane B: DynamX ^® POLYMER National Starch, INCI name: Polyurethane 14 (and) AMP-acrylate copolymer, polyurethanes-14 consists of isophoronediisocyanates, propylene glycol, dimethyl propanoic acid, diol, polyether.
Polyurethane C Inventive hair cosmetic composition prepared in Example 3 Acrylate Polymer: AMPHOMER ^® POLYMER the company National Starch, INCI name: Octylacrylamide / Acrylates / Butylaminoethyl / methacrylate copolymer.

The experiments show that the hair cosmetic composition according to the invention leads to a significantly lower combing power in comparison to polyurethanes or polyacrylates known from the prior art. Even doubling the amount applied (12 sprays) does not lead to a strong increase in combing power.

FORMULATION EXAMPLES:

All amounts, proportions and percentages are, unless stated otherwise, based on the weight and the total amount or on the total weight of the compositions.

The parts by weight of the dispersion of the invention are based on solids. Pump-setting spray: A B Polyurethane polyurea / nitrocellulose dispersion according to the invention 2 10 ethanol 55 30 Perfume qs qs water ad 100 Ad 100 Aerosol Hair Spray: C D e F G Polyurethane-polyurea / nitrocellulose dispersion according to the invention 5 10 2 5 8th Octyl acrylamide / acrylates / butylaminoethyl methacrylates (based on solids) 1.8 Acrylates Copolymer ¹ 2 amino methyl propanol q. s q. s glycerin 0.5 panthenol 0.5 0.5 PEG / PPG-18/18 Dimethicone 0.5 PEG-12 dimethicone 0.05 Propylene glycol 0.5 Cyclomethicone 1.0 1.0 Benzophenone-3 0.1 0.1 0.1 Perfume q. s q. s q. s q. s q. s ethanol 14.5 20 60 30 20 water ad 100 ad 100 ad 100 ad 100 ad 100 Propane / butane 3.5 bar (20 ° C) 20 10 dimethyl ether 40 30 30 20 Hydrofluorocarbon 152 A 20 ¹ Luvimer P-100, BASF hair foam: H I Polyurethane polyurea / nitrocellulose dispersion according to the invention 2 4 glycerin 0.1 panthenol 0.05 0.5 Polyquaternium-4 2 cetyltrimethylammonium 0.2 0.5 PEG-12 dimethicone 0.5 Cyclomethicone 0.5 Benzophenone-3 0.1 Perfume qs qs ethanol 15 10 water ad 100 ad 100 preservative qs qs dimethyl ether 10 7 Hydrofluorocarbon 152 A 3 Hair gel / cream: J K L Polyurethane polyurea / nitrocellulose dispersion according to the invention 5 2 8th Carbomer 0.8 Acrylic Acid / VP Copolymer 0.5 Ammonium acryloyldimethyltaurate / VP copolymer 0.8 glycerin 0.5 panthenol 0.5 0.5 propylene glycol 0.2 Cyclomethicone 0.2 neutralizer qs qs qs Perfume qs qs qs ethanol 20 water ad. 100 ad. 100 ad. 100 preservative qs qs qs

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1049446 A [0008]
• EP 1049443 A [0008]
• DE 2446440 A [0047]
• EP 0916647 A [0062, 0064]
• WO 01/88006 A [0062]
• US 3836537 [0109]
• FR 1400366 [0109]

Cited non-patent literature

• Aerosol and Spray Report, Vol. 37, n ° 3, 1998, 20-23 [0007]
• Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim, pp. 31-38 [0050]
• ISO 14446 [0081]
• ISO 14446 [0081]
• ISO 14446 [0081]
• DIN EN ISO 3251 [0090]
• DIN EN ISO 3251 [0138]
• DIN EN ISO 11909 [0139]

Claims (10)

Use of a composition comprising nitrocellulose-polyurethane-polyurea particles as hair cosmetics. Use according to claim 1, characterized in that the nitrocellulose polyurethane polyurea particles have been added to the composition in the form of an aqueous dispersion of nitrocellulose polyurethane polyurea particles. Use according to claim 2, characterized in that the aqueous dispersion of nitrocellulose polyurethane polyurea particles is obtainable by a process comprising the steps of: A) Preparation of one or more isocyanate-functional prepolymers A1) one or more organic polyisocyanates A2) one or more polymeric polyols having number-average molecular weights of from 400 to 8000 g / mol, A3) optionally one or more hydroxy-functional compounds having molecular weights of 62 to 399 g / mol and A4) optionally one or more isocyanate-reactive, anionic, potentially anionic and / or nonionic hydrophilicizing agents, B) reacting the free NCO groups of the prepolymers from step A) with one or more amino-functional compounds, C) dispersing the prepolymers from step A) or the reaction products with amino-functional compounds from step B) in water, D) adding nitrocellulose in the form of a solution in an organic solvent or a mixture of solvents, and E) removal of organic solvent. Use according to one of the preceding claims, characterized in that the nitrocellulose-polyurethane polyurea particles have an average particle size of 20 to 700 nm, measured by means of laser correlation spectroscopy. Use according to one of the preceding claims, characterized in that the concentration of the nitrocellulose polyurethane polyurea particles in the range of 0.1 to 20 wt .-% and preferably in the range of 0.5 to 10 wt .-%, each based on the Total weight of the composition is. Use according to one of the preceding claims, characterized in that the composition contains at least one cosmetically acceptable distribution medium. Use according to one of the preceding claims, characterized in that the composition contains at least one further cosmetically active ingredient. Use according to one of the preceding claims, characterized in that the composition contains at least one further film former. Use according to any one of the preceding claims, characterized in that the composition has a volatile organic content of less than 80% by weight of the composition. A method of styling or strengthening the hair comprising applying to the hair a composition containing nitrocellulose-polyurethane-polyurea particles.