DE10311120A1 - Polymer products especially for use as hair styling agents or conditioners are obtained by mixing a silicone with a product obtained by polymerizing an unsaturated monomer in presence of an unsaturated polyalkyleneglycol - Google Patents

Abstract

Production of polymer products involves mixing at >=30[deg]C (a) a polymer obtained by polymerizing an ethylenically unsaturated monomer in presence of unsaturated polyalkyleneglycols; and (b) silicones. An independent claim is also included for the products thus obtained.

Description

The present invention relates to polymeric products, a process for their preparation and the Use of the polymeric products in cosmetic, in particular hair cosmetic preparations.

Polymers with film-forming properties be for used cosmetic and / or pharmaceutical preparations and are particularly suitable as additives for hair and skin cosmetics.

In cosmetic preparations for the skin can Polymers have a special effect. The polymers can under other to keep the skin moisturized and conditioned and to improve it of the skin feeling contribute. The skin becomes smoother and more supple.

In cosmetic preparations for the hair become polymers for strengthening, structural improvement and shaping of hair used. You increase combability and improve the feel of the hair. These hair treatment products generally contain a solution of the film former in an alcohol or a mixture of alcohol and water.

A requirement for hair treatment products is to give the hair shine, flexibility and a natural, pleasant feel to lend. The wished Property profile includes strong consolidation at high humidity, Elasticity, Washability of the hair and compatibility with the other formulation components.

DE 42 40 108 describes polysiloxane-containing binders which are suitable as dirt-repellent coatings, in particular as anti-graffiti coatings. However, these binders are varnish-like and are not suitable for cosmetic purposes.

DE 16 45 569 describes a process for the preparation of organosilicon graft copolymers and their use as foam compositions.

EP 0 953 015 describes amphiphilic polymers in combination with alkoxylated silicones.

JP 06-192048 describes copolymers of (meth) acrylamide-based monomers in combination with polyoxyalkylated siloxanes.

JP 10-226627 describes amphoteric polymers in combination with polyoxyalkylated siloxanes.

EP 0 852 488 B1 describes cosmetic compositions which contain a silicone-containing graft polymer in combination with at least one further silicone.

Object of the present invention was the provision of polymeric products, which in particular for hair cosmetics Own preparations. The combination was of particular importance various advantageous properties such as strong consolidation high humidity, elasticity, washability from the hair and tolerance with the rest Formulation components. Furthermore, the products are intended for the hair Shine, flexibility and natural, give a comfortable grip.

• (A) Polymerisaten, die erhältlich sind durch radikalische Polymerisation von (A-1) ethylenisch ungesättigten Monomeren in Gegenwart von (A-2) ungesättigten Polyalkylenglykolen mit
• (B) Silikonen

bei einer Temperatur größer gleich 30 °C.The object of the invention is achieved by polymeric products which are obtainable by mixing

• (A) Polymers which are obtainable by free-radical polymerization of (A-1) ethylenically unsaturated monomers in the presence of (A-2) unsaturated polyalkylene glycols
• (B) silicones

at a temperature greater than or equal to 30 ° C.

In a particularly preferred embodiment are used as silicones (B) compounds that are selected from the group consisting of (B-1) silicones with at least one quaternized or non-quaternized amine function, (B-2) silicone resins, (B-3) silicone rubbers, (B-4) polyalkoxylated silicones and / or (B-5) silicone-containing polyurethanes (B-5).

All indices mentioned below and substituents each refer to the formulas in the text stand right in front.

Ethylenically unsaturated monomers (A-1)

As suitable polymerizable monomers (A-1) become ethylenically unsaturated Monomers used. You can either single monomers or combinations of two or more Monomers are used.

Monomers with a through free Radically initiated reaction can be polymerized prefers. The term ethylenically unsaturated means that the monomers at least one polymerizable carbon-carbon double bond possess, which can be mono-, di-, tri-, or tetrasubstituted.

By polymerizable is meant that the monomers used using any conventional synthetic method can be polymerized.

The ethylenically unsaturated monomers (A-1) can be described by the following general formula: XC (O) CR ⁷ = CHR ⁶ in which
X is selected from the group consisting of -OH, -OM, -OR ⁸ , NH ₂ , -NHR ⁸ , N (R ^B ) ₂ ;
M is a cation selected from the group consisting of: Na +, K +, Mg ++, Ca ++, Zn ++, NH4 +, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium;
the radicals R ⁸ can be selected identically or differently from the group consisting of -H, C1-C40 linear or branched-chain alkyl radicals, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl or ethoxypropyl ,

R ⁷ and R ⁶ are independently selected from the group consisting of: -H, C ₁ -C ₈ linear or branched chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.

Representative but not limiting Examples of suitable monomers (A-1) are, for example, acrylic acid and their salts, esters and amides. The salts cannot from any toxic metal, ammonium or substituted ammonium counterions be derived.

The esters can be derived from C ₁ -C _{4 0} linear, branched C ₃ -C _{4 0,} or C ₃ -C _{4 0} carbocyclic alcohols, from polyfunctional alcohols having 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol and 1 , 2,6-hexanetriol, from amino alcohols or from alcohol ethers such as methoxyethanol and ethoxyethanol or polyethylene glycols.

mit R⁹ = H, Alkyl mit 1 bis 8 C-Atomen,
R¹⁰ = H, Methyl,
R¹¹ = Alkylen mit 1 bis 24 C-Atomen, optional substituiert durch Alkyl,
R^{1 2}, R^{1 3} = C₁-C₄₀ Alkylrest,
Z = Stickstoff für x = 1 oder Sauerstoff für x = 0Also suitable are N, N-dialkylaminoalkyl acrylates and methacrylates and N-dialkylaminoalkyl acrylates and methacrylamides of the general formula (II)

with R ⁹ = H, alkyl with 1 to 8 C atoms,
R ¹⁰ = H, methyl,
R ¹¹ = alkylene with 1 to 24 carbon atoms, optionally substituted by alkyl,
R ^{1 2} , R ^{1 3} = C ₁ -C ₄₀ alkyl radical,
Z = nitrogen for x = 1 or oxygen for x = 0

The amides can be unsubstituted, N-alkyl or N-alkylamino monosubstituted, or N, N-dialkyl-substituted or N, N-dialkylamino disubstituted, wherein the alkyl or alkylamino groups of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched, or C3-C40 carbocyclic units are derived. In addition, the alkylamino groups can be quaternized.

Preferred monomers of formula II are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate.

Monomers (A-1) which can also be used are substituted acrylic acids and salts, esters and amides thereof, where the substituents on the carbon atoms are in the two or three positions of acrylic acid and are selected independently of one another from the group consisting of C ₁ -C ₄ Alkyl, -CN, COOH particularly preferably methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid. These salts, esters and amides of these substituted acrylic acids can be selected as described above for the salts, esters and amides of acrylic acid.

Other suitable monomers (A-1) are vinyl and allyl esters of C ₁ -C _{4 0} linear, branched C ₃ -C _40, or C ₃ -C ₄₀ carbocyclic carboxylic acids (eg, vinyl acetate, vinyl propionate, vinyl neononanoate, Vinylneoundekansäure or t-butyl -benzoesäurevinylester); Vinyl or allyl halides, preferably vinyl chloride and allyl chloride, vinyl ethers, preferably methyl, ethyl, butyl or dodecyl vinyl ether, vinylformamide, vinyl methylacetamide, vinylamine; Vinyl lactams, preferably vinyl pyrrolidone and vinyl caprolactam, vinyl or allyl-substituted heterocyclic compounds, preferably vinyl pyridine, vinyl axazoline and allyl pyridine.

Also suitable are N-vinylimidazoles of the general formula III, in which R ^{1 4} to R ^{1 6} independently of one another are hydrogen, C ₁ -C ₄ -alkyl or phenyl:

mit R¹⁷ = C₁-C₂₄ AlkylFurther suitable monomers (A-1) are diallylamines of the general formula (IV)

with R ¹⁷ = C ₁ -C ₂₄ alkyl

Other suitable monomers (A-1) are vinylidene chloride; and hydrocarbons with at least one Carbon-carbon double bond, preferably styrene, alpha-methylstyrene, tert-butylstyrene, Butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, Vinyl toluene, and mixtures of these monomers.

Particularly suitable monomers (A-1) are acrylic acid, methacrylic acid, ethyl acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, propyl methacrylate -Butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butylethacrylate, iso-butylethacrylate, t-butyl ethacrylate, 2-ethylhexylethacrylate, decylethacrylate, 2,3-dihydroxypropyl hydroxyl acrylate, 2,3-diacrylate -Hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, such as glyceryl monoacrylate, methacrylate, such as glyceryl monoacrylate, methacrylate, such as glyceryl mono acrylate, acrylamidopropanesulfonic;
Acrylamide, methacrylamide, ethacrylamide, N-methyl acrylamide, N, N-dimethylacrylamide, N-ethyl acrylamide, N-isopropylacrylamide, N-butylacrylamide, Nt-butylacrylamide, N-octylacrylamide, Nt-octylacrylamide, N-octadecylacrylamide, N-phenylacrylamide methyl methacrylamide; N-ethyl methacrylamide, N-dodecyl methacrylamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate, N, N-Dimethylaminododecyl (meth) acrylate, N- [3- (dimethylamino) propyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N- [8 - (dimethylamino) octyl] methacrylamide, N- [12- (dimethylamino) dodecyl] methacrylamide, N- [3- (diethylamino) propyl] methacrylamide, N- [3- (diethylamino) propyl] acrylamide;
Maleic acid, fumaric acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, diallyldimethylammonium chloride, vinyl ether (for example: methyl, ethyl, butyl or dodecyl vinyl ether), vinyl formamide, vinyl methylacetamide, vinylamine; Methyl vinyl ketone, maleimide, vinyl pyridine, vinyl imidazole, vinyl furan, styrene, styrene sulfonate, allyl alcohol, and mixtures thereof.

Of these, particularly preferred Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic, maleic anhydride as well as its half esters, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, N-t-butyl acrylamide, N-octylacrylamide, 2-hydroxyethyl acrylate, Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, Alkylene glycol (meth) acrylates, unsaturated sulfonic acids such as for example acrylamidopropanesulfonic acid, vinyl pyrrolidone, vinyl caprolactam, Vinyl ether (e.g. methyl, ethyl, butyl, or dodecyl vinyl ether), Vinylformamide, vinylmethylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N, N-dimethylaminomethyl methacrylate and N- [3- (dimethylamino) propyl] methacrylamide; 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide quaternized with methyl chloride, Methyl sulfate or diethyl sulfate.

In a very particularly preferred embodiment are used as monomers (A-1) t-butyl acrylate and methacrylic acid.

Monomers with a basic nitrogen atom can be quaternized in the following way:
For quaternization of the amines, for example, alkyl halides with 1 to 24 carbon atoms in the alkyl group are suitable, for example methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, in particular benzyl chloride and benzyl bromide. Other suitable quaternizing agents are dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate. The quaternization of the basic amines can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids. Preferred quaternizing agents are: methyl chloride, dimethyl sulfate or diethyl sulfate.

In a preferred embodiment are used as monomers (A-1) (meth) acrylates.

The quaternization can be done before Polymerization or be carried out after the polymerization.

In addition, the reaction products of unsaturated acids, such as acrylic acid or methacrylic acid, with a quaternized epichlorohydrin of the general formula (V) can be used (R ^{1 8} = C 1 to C 40 alkyl).

Examples include:
(Meth) acryloyloxyhydroxypropyltrimethylammonium chloride and
(Meth) acryloyloxyhydroxypropyltriethylammonium chloride.

The basic monomers can too can be cationized by mixing with mineral acids, e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or with organic acids, such as. formic acid, Acetic acid, Lactic acid, or citric acid, be neutralized.

In addition to the above-mentioned monomers, so-called macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers can be used as monomers (A-1), as described, for example, in US Pat EP 408 311 are described.

Furthermore, fluorine-containing monomers such as those in the EP 558 423 are described, crosslinking or regulating the molecular weight compounds are used in combination or alone.

Unsaturated polyalkylene glycols (A-2)

• – die Gruppen M, die identisch oder voneinander verschieden sind, Wasserstoff, Na, K, Li, NH₄ oder ein organisches Amin bedeuten,
• – R⁷ Wasserstoff oder SO₃M ist,
• – d im Bereich von 1 bis 10 liegt,
• – s 0, 1 bis 10 sein kann
• – t 0, 1 bis 10 sein kann
• – a im Bereich von 0 bis 50 liegt,
• – b im Bereich von 0 bis 50 liegt,
• – a + b größer 0 ist,
• – c 0, 1, 2, 3 oder 4 ist,
• – Y ein einwertiges anorganisches oder organisches Anion bedeutet.

Unsaturated polyalkylene glycols of the general formula are suitable as compounds (A-2) H ₂ C = CH-C _c H _{2 c} -O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -R ⁵ and or H ₂ C = CH-C _c H _{2 c} -O- (C ₄ H ₈ O) _a -R ⁵ wherein
R ⁵ denotes -H, -CH = CH ₂ , - (CH ₂ ) _s -CH = CH- (CH ₂ ) _t -H, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, a straight-chain or branched alkoxy group with 1 to 6 carbon atoms, a straight-chain or branched acyl group with 2 to 40 carbon atoms, -SO ₃ M, a C _{1 -6} -aminoacyl group optionally substituted on the amino group, -NHCH ₂ CH ₂ COOM, -N (CH ₂ CH ₂ COOM) ₂ , an optionally substituted on the amino group and aminoalkyl group on the alkyl group, a C _{2-3 0} -Carboxyacylgruppe, optionally substituted with one or two substituted aminoalkyl phosphono, -CO (CH _{2) d} COOM, -COOHR ⁷ (CH _{2) d} COOM , -NHCO (CH ₂ ) _d ON, -NH ₂ Y or a phosphate group

• The groups M, which are identical or different from one another, denote hydrogen, Na, K, Li, NH ₄ or an organic amine,
• - R ^{7 is} hydrogen or SO ₃ M,
• - d is in the range from 1 to 10,
• - s can be 0, 1 to 10
• - t can be 0.1 to 10
• A is in the range from 0 to 50,
• B is in the range from 0 to 50,
• - a + b is greater than 0,
• - c is 0, 1, 2, 3 or 4,
• - Y is a monovalent inorganic or organic anion.

Compounds (A-2) with R ⁵ = H and / or a straight-chain or branched alkyl group with 1 to 12 carbon atoms, in particular -CN ₃ and -C ₂ H ₅ , are particularly preferred.

Compounds are particularly preferred (A-2) with c = 1.

Compounds (A-2) with R ⁵ = H and R ⁵ = -CH ₃ are particularly preferred.

Compounds (A-2) with R ⁵ = N and c = 1 are particularly preferred

Compounds (A-2) with R ⁵ = -CH ₃ and c = 1 are particularly preferred. Compounds (A-2) are commercially available, for example, under the trade names Pluriol from BASF AG. Examples include the products Pluriol ^® A 10 R and Pluriol ^® A 11 R.

The connections are also suitable, the under the CAS no. 272 74-31-3 as polyalkylene glycol monoallyl ether or under CAS No. 126682-74-4 as polyalkylene glycol monovinyl ethers from Clanant are available (designation A- and V-type polyglycols from Clariant).

Silicones (B)

As silicones (B) are principal all silicone compounds suitable. Non-volatile silicones are particularly suitable. Nonvolatile Silicones are such compounds with a boiling point below 100 ° C, in particular below 90 ° C. Water-soluble or water-dispersible are particularly suitable Silicones.

For the purposes of the invention, "water-dispersible" means silicones meant that in contact with water within 24 hours Form fluid that is not fixed to the eye without optical aids Particles can be recognized. To check whether a silicone is water dispersible, 100 mg of the silicone in the form of a 100 mm thick film in 100 ml of water (20 ° C) and on a commercially available Shake table for 24 hours shaken. If after shaking no more solid particles can be seen, but the fluid is cloudy, the silicone is water dispersible; without cloudiness it is said to be water soluble.

In a preferred embodiment Compounds that are selected are used as silicones from the group consisting of (B-1) silicones with at least one quaternized or non-quaternized amine function, (B-2) silicone resins, (B- 3) silicone rubbers, (B-4) polyalkoxylated silicones and / or (B-5) silicone-containing Polyurethanes. Of course can both mixtures of compounds within individual groups (e.g. 2 compounds from B-4) and mixtures of compounds from different groups can be used (a compound of B-1 and one or more Connections from e.g. B-4).

(B-1) Silicones with at least a quaternized or non-quaternized amine function

• (a) die Silikonpolymere, die der folgenden Formel (II) entsprechen: R¹ _aG¹ _{3 -a}-Si(OSiG² ₂)_n-(OSiG³ _bR² _2-b)_m-O-SiG⁴ _3-a-R³ _a' (II) in der: G¹, G², G³ und G⁴, die identisch oder verschieden sind, ein Wasserstoffatom, eine Phenylgruppe, OH, C₁-C₁₈-Alkyl, beispielsweise Methyl, C₂-C_{1 8}-Alkenyl oder C₁-C₁₈-Alkoxy bedeuten; a, a', die identisch oder verschieden sind, 0 oder eine ganze Zahl von 1 bis 3, insbesondere 0 bedeuten; b 0 oder 1 und insbesondere 1 bedeutet; m und n Zahlen bedeuten, deren Summe (n + m) besonders zwischen 1 und 2000 und insbesondere zwischen 50 und 150 variieren kann, wobei n eine Zahl von 0 bis 1999 und besonders von 49 bis 149 und m eine Zahl von 1 bis 2000, besonders von 1 bis 10 bedeuten kann; R¹, R², R³, R⁴, die identisch oder verschieden sind, ein einwertiges Radikal der Formel C_qH_2qO_sR⁵ _tL bedeuten, in der q eine Zahl von 1 bis 8 ist, s und t, die identisch oder verschieden sind, gleich 0 oder 1 sind, R⁵ eine gegebenenfalls hydroxylierte Alklyengruppe und L eine gegebenenfalls quaternisierte aminierte Gruppe ist, die aus den folgenden Gruppen gewählt wird: in denen R'' Wasserstoff, Phenyl, Benzyl oder ein einwertiges gesättigtes Kohlenwasserstoffradikal bedeuten kann, z. B. ein Alkylradikal mit 1 bis 20 Kohlenstoffatomen, und A^– ein Halogenid-Ion, wie z.B. Fluorid, Chlorid, Bromid oder Iodid. – NR''-CH₂-CH₂-N'(R'')₂ – N(R'')₂ – N^/(R'')₃A^– – N^/(R'')₂A^– – N^/H₂(R'')A^– – N(R'')-CH₂-CH₂-N^/R''H₂A^–,
• (b) die Verbindungen der Formel (III): NH-[(CH₂)₃-Si[OSi(CH₃)₃]]₃ (III)

Among the silicones which contain at least one amino group, quaternized or not, the following can be mentioned:

• (a) the silicone polymers corresponding to the following formula (II): R ¹ _a G ¹ _{3 -a} -Si (OSiG ² ₂ ) _n - (OSiG ³ _b R ² _2-b ) _m -O-SiG ⁴ _3-a -R ³ _{a '} (II) in which: G ¹ , G ² , G ³ and G ⁴ , which are identical or different, represent a hydrogen atom, a phenyl group, OH, C ₁ -C ₁₈ alkyl, for example methyl, C ₂ -C _{1 8} alkenyl or C ₁ -C ₁₈ alkoxy; a, a ', which are identical or different, represent 0 or an integer from 1 to 3, in particular 0; b represents 0 or 1 and in particular 1; m and n are numbers, the sum (n + m) of which can vary in particular between 1 and 2000 and in particular between 50 and 150, where n is a number from 0 to 1999 and in particular from 49 to 149 and m is a number from 1 to 2000, can particularly mean from 1 to 10; R ¹ , R ² , R ³ , R ⁴ , which are identical or different, denote a monovalent radical of the formula C _q H _2q O _s R ⁵ _t L, in which q is a number from 1 to 8, s and t, which are identical or different, are 0 or 1, R ^{5 is} an optionally hydroxylated alkylene group and L is an optionally quaternized aminated group which is selected from the following groups: in which R ″ is hydrogen, phenyl, benzyl or a monovalent saturated hydrocarbon radical can mean e.g. B. an alkyl radical with 1 to 20 carbon atoms, and A ^- a halide ion, such as fluoride, chloride, bromide or iodide. - NR '' - CH ₂ -CH ₂ -N '(R'') ₂ - N (R'') ₂ - N ^/ (R'') ₃ A ^- - N ^/ (R'') ₂ A ^- - N ^/ H ₂ (R '') A ^- - N (R '') - CH ₂ -CH ₂ -N ^/ R''H ₂ A ^- ,
• (b) the compounds of the formula (III): NH - [(CH ₂ ) ₃ -Si [OSi (CH ₃ ) ₃ ]] ₃ (III)

in der x' und y' ganze Zahlen sind, die vom Molekulargewicht abhängen und im allgemeinen solche, deren Molekulargewicht zwischen 5000 und ungefähr 20000 liegt. Ein Produkt, das der Formel (II) entspricht, ist das in der CTFA-Nomenklatur als „Trimethylsilylamodimethicone" benannte Polymer, das der Formel (V) entspricht:

in der n und m die oben angegebenen Bedeutungen haben (vgl. Formel II).This compound corresponds to the CTFA name "Amino-bis-propyldimethicone". The products corresponding to formula (II) are e.g. B. the polysiloxanes, which are referred to in the CTFA nomenclature as "amodimethicones" and correspond to the following formula (IV):

in which x 'and y' are integers which depend on the molecular weight and generally those whose molecular weight is between 5000 and approximately 20,000. A product that corresponds to formula (II) is the polymer named "trimethylsilylamodimethicone" in the CTFA nomenclature and corresponds to formula (V):

in which n and m have the meanings given above (cf. Formula II).

A commercial product which corresponds to this definition is a mixture (90/10% by weight) of a polydimethylsiloxane with aminoethyl-aminoisobutyl groups and a polydimethylsiloxane, which is sold under the name Q2-8220 by DOW CORNING. Such polymers are described, for example, in the patent application EP-A-95238 described.

in der:
R⁷ für ein einwertiges Kohlenwasserstoffradikal mit 1 bis 18 Kohlenstoffatomen und insbesondere einem C₁-C₁₈-Alkylradikal oder C₂-C₁₈-Alkenylradikal, z. B. Methyl, steht;
R⁸ für ein zweiwertiges Kohlenwasserstoffradikal, besonders ein C₁-C₁₈-Alkylenradikal oder ein zweiwertiges C₁-C₁₈-Alkenoxyradikal, z. B. C₁-C₈, steht;
Q^– ein Halogenid-Ion, insbesondere Chlorid ist;
r für einen statistischen Mittelwert von 2 bis 20 und insbesondere von 2 bis 8 steht;
s für einen statistischen Mittelwert von 20 bis 200 und insbesondere von 20 bis 50 steht.Other polymers corresponding to formula (II) are silicone polymers of the formula:

in the:
R ^{7 is} a monovalent hydrocarbon radical having 1 to 18 carbon atoms and in particular a C ₁ -C ₁₈ alkyl radical or C ₂ -C ₁₈ alkenyl radical, e.g. B. methyl;
R ⁸ for a divalent hydrocarbon radical, especially a C ₁ -C ₁₈ alkylene radical or a divalent C ₁ -C ₁₈ alkenoxy radical, e.g. B. C ₁ -C ₈ ;
Q ^{- is} a halide ion, especially chloride;
r represents a statistical mean of 2 to 20 and in particular 2 to 8;
s stands for a statistical mean of 20 to 200 and in particular 20 to 50.

Such polymers are particularly mentioned in the patent US 4 185 087 described.

in der R⁹ Alkenyl- und/oder Alkylradikale mit 14 bis 22 Kohlenstoffatomen, Derivate der Talgfettsäuren, bedeuten, gemeinsam mit einem nicht ionischen Tensid der Formel: C₉H_{1 9}-C₆H₄-(OC₂H₄)₁₀-OH, bekannt unter der CTFA-Nomenklatur "Nonoxynol 10".A polymer corresponding to formula (III) is the polymer sold by Union Carbide under the name "Ucar Silicone ALE 56". If these silicone polymers are used, a particularly interesting embodiment is their use together with cationic and / or non-ionic surfactants. For example, the product sold by DOW CORNING under the name "Emulsion Cationique DC 929" can be used which, in addition to the amodimethicone, contains a cationic surfactant which contains a mixture of products according to the following formula:

in which R ⁹ is alkenyl and / or alkyl radicals having 14 to 22 carbon atoms, derivatives of tallow fatty acids, mean, together with a nonionic surfactant of formula: C ₉ H _{1 9} -C ₆ H ₄ - (OC ₂ H _{4) 10} - OH, known under the CTFA nomenclature "Nonoxynol 10".

Another commercial product which can be used according to the invention is the product which is marketed under the name “Dow Corning Q2 7224” by Dow Corning, which together with the trimethylsilylamodimethicone of the formula M is a nonionic surfactant of the formula: C ₈ H ₁₇ -C ₆ H ₄ - (OCH ₂ CH ₂ ) _n -OH, where n = 40, otherwise referred to as octoxynol-40, another nonionic surfactant of the formula: C ₁₂ H ₂₅ - (OCH ₂ -CH ₂ ) _n -OH, wherein n = 6, otherwise referred to as Isolaureth-6, and contains glycol.

(B-2) silicone resins

The inventively used silicone resins are crosslinked siloxane systems containing the units: R ² SiO _2/2, RSiO _3/2, and SiO _4/2 included in which R groups of substances a hydrocarbon, having from 1 to 6 carbon atoms, or a phenyl group. Among these products, those in which R is a lower alkyl radical (C ₁ -C ₆ ) or a phenyl radical are particularly preferred.

Among these resins, the product sold under the name "DOW CORNING 593" or those products sold under the names "SILICONE FLUID SS 4230" and SS 4267 ⁴ by the company GENERAL ELECTRIC and the "Dimethyl / Trimethylpolysiloxanes ".

(B-3) silicone rubbers

The silicone rubber (B-3) according to the invention are Polydiorganosiloxanes of high molecular masses between 200,000 and 2,000,000, alone or as a mixture in a solvent used that from the volatile Silicones, the polydimethylsiloxane oils, the polymethylphenylsiloxane or the polydiphenyldimethylsiloxane oils, isoparaffins, methylene chloride, pentane, hydrocarbons or selected their mixtures becomes.

One is preferably used Silicone rubber with a molecular weight below 1,500,000. The silicone rubber are e.g. a polydimethylsiloxane, a polyphenylmethylsiloxane, a poly (diphenylsiloxane-dimethylsiloxane), a poly (dimethylsiloxane methylvinylsiloxane), a poly (dimethylsiloxane-phenylmethylsiloxane), a poly (diphenylsiloxane dimethylsiloxane-methylvinylsiloxane). This Silicone rubber can Complete at the end of the chain with trimethylsilyl or dimethylhydroxysilyl groups.

in der:
R¹, R², R⁵ und R⁶ gemeinsam oder getrennt ein Alkylradikal mit 1 bis 6 Kohlenstoffatomen sind,
R³ und R⁴ gemeinsam oder getrennt ein Alkylradikal mit 1 bis 6 Kohlenstoffatomen oder ein Arylrest sind,
X ein Alkylrest mit 1 bis 6 Kohlenstoffatomen, ein Hydroxylrest oder ein Vinylradikal ist,
wobei n und p derart ausgewählt werden, dass der Silikongummi eine Viskosität höher als 100 000 mPa·s, vorzugsweise höher als 500 000 mPa·s, aufweist.In particular, a silicone rubber can be used which corresponds to the formula (VI):

in the:
R ¹ , R ² , R ⁵ and R ⁶ together or separately are an alkyl radical with 1 to 6 carbon atoms,
R ³ and R ⁴ together or separately are an alkyl radical with 1 to 6 carbon atoms or an aryl radical,
X is an alkyl radical with 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,
where n and p are selected such that the silicone rubber has a viscosity higher than 100,000 mPa · s, preferably higher than 500,000 mPa · s.

In general, n and p can have values from 0 to 5000, preferably from 0 to 3000. The silicone rubber can be incorporated in the composition as it is or in a silicone oil dissolved form, such as a volatile or non-volatile PDMS (polydimethylsiloxane).

• – die Substituenten R¹ bis R⁶ und X eine Methylgruppe bedeuten, p = 0 und n = 2700 ist, wie jener, der unter der Bezeichnung SE30 durch die Gesellschaft General Electric vertrieben wird,
• – die Substituenten R¹ bis R⁶ und X eine Methylgruppe bedeuten, p = 0 und n = 2300 ist, wie jener, der unter der Bezeichnung AK 500000 durch die Gesellschaft Waker vertrieben wird,
• – die Substituenten R¹ bis R⁶ eine Methylgruppe bedeuten, der Substituent X eine Hydroxylgruppe bedeutet, p = 0 und n = 2700 ist, in einer 13%igen Lösung in Cyclopentasiloxan, wie jener, der unter der Bezeichnung Q2-1401 durch die Gesellschaft DOW CORNING vertrieben wird,
• – die Substituenten R¹ bis R⁶ eine Methylgruppe bedeuten, der Substituent X eine Hydroxylgruppe bedeutet, p = 0 und n = 2700 ist, in einer 13%igen Lösung in Dimethicon, wie jener, der unter der Bezeichnung Q2-1403 durch die Gesellschaft DOW CORNING vertrieben wird,
• – die Substituenten R₁, R₂, R₅, R₆ und X eine Methylgruppe bedeuten, die Substituenten R³ und R⁴ eine Arylgruppe bedeuten, so wie das Molekulargewicht der Verbindung 600 000 ist, wie jener, der unter der Bezeichnung 761 durch die Gesellschaft RHONE-POULENC vertrieben wird.

As silicone rubber which can be used according to the invention, there can be mentioned those in which:

• The substituents R ¹ to R ⁶ and X represent a methyl group, p = 0 and n = 2700, such as that sold by General Electric under the name SE30,
• The substituents R ¹ to R ⁶ and X represent a methyl group, p = 0 and n = 2300, such as that which is marketed by the Waker company under the name AK 500000,
• - The substituents R ¹ to R ^{6 represent} a methyl group, the substituent X represents a hydroxyl group, p = 0 and n = 2700, in a 13% solution in cyclopentasiloxane, such as that sold by the company under the name Q2-1401 DOW CORNING is distributed,
• - the substituents R ¹ to R ⁶ denote a methyl group, the substituent X denotes a hydroxyl group, p = 0 and n = 2700, in a 13% solution in dimethicone, such as that sold by the company under the name Q2-1403 DOW CORNING is distributed,
• The substituents R ₁ , R ₂ , R ₅ , R ₆ and X denote a methyl group, the substituents R ³ and R ⁴ denote an aryl group, such as the molecular weight of the compound is 600,000, such as that described under the name 761 by RHONE-POULENC is distributed.

(B-4) golyalkoxylated silicones

wobei in den Formeln B-4a), B-4b) und B-4c)

• – die Gruppen R¹, die identisch oder voneinander verschieden sind, eine geradkettige oder verzweigte C_1-30-Alkylgruppe oder eine Phenylgruppe, insbesondere -CH₃ bedeuten
• – die Gruppen R², die identisch oder voneinander verschieden sind, R¹ oder eine Gruppe -C_cH_{2 c}-O-(C₂H₄O)_a(C₃H₆O)b-R⁵ oder eine Gruppe C_cH_{2 c}-O-(C₄H₈O)_a-R⁵ bedeuten mit der Maßgabe, dass mindestens einer der Reste R² eine Gruppe -C_cH_{2 c}-O-(C₂H₄O)_a(C₃H₆O)_b-R⁵ oder eine Gruppe C_cH_{2 c}-O-(C₄H₈O)_a-R⁵ bedeuten,
• – die Gruppen R³ und R⁴, die identisch oder voneinander verschieden sind, eine geradkettige oder verzweigte C_1-12-Alkylgruppe und vorzugsweise Methyl bedeuten,
• – die Gruppen R⁵, die identisch oder voneinander verschieden sind, ausgewählt unter einem Wasserstoffatom, einer geradkettigen oder verzweigten Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, einer geradkettigen oder verzweigten Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, einer geradkettigen oder verzweigten Acylgruppe mit 2 bis 40 Kohlenstoffatomen, -SO₃M, einer gegebenenfalls an der Aminogruppe substituierten C_1-6-Aminoalkoxygruppe, einer gegebenenfalls an der Aminogruppe substituierten C_2-6-Aminoacylgruppe, -NHCH₂CH₂COOM, -N(CH₂CH₂COOM)₂, einer gegebenenfalls an der Aminogruppe und an der Alkylgruppe substituierten Aminoalkylgruppe, einer C_{2-3 0}-Carboxyacylgruppe, einer gegebenenfalls mit einer oder zwei substituierten Aminoalkylgruppen substituierten Phosphonogruppe, -CO(CH₂)_dCOOM, -COCHR₇(CH₂)_dCOOM, -NHCO(CH₂)_dOH, -NH₃Y oder einer Phosphatgruppe ausgewählt sind,
• – die Gruppen M, die identisch oder voneinander verschieden sind, Wasserstoff, Na, K, Li, NH₄ oder ein organisches Amin bedeuten,
• – R₇ Wasserstoff oder SO₃M ist,
• – d im Bereich von 1 bis 10 liegt,
• – m im Bereich von 0 bis 20 liegt,
• – n im Bereich von 0 bis 500 liegt,
• – o im Bereich von 0 bis 20 liegt,
• – p im Bereich von 1 bis 50 liegt,
• – a im Bereich von 0 bis 50 liegt,
• – b im Bereich von 0 bis 50 liegt,
• – a + b mindestens 2 bedeutet,
• – c im Bereich von 0 bis 4 liegt,
• – x im Bereich von 1 bis 100 liegt, und
• – Y ein einwertiges anorganisches oder organisches Anion bedeutet,

mit der Maßgabe, dass n über 12 liegt, wenn das Silicon die Formel (II) mit R₅ = Wasserstoff bedeutet.Polyalkoxylated silicones (B-4) are compounds which are selected from the compounds of the general formulas:

where in formulas B-4a), B-4b) and B-4c)

• - The groups R ¹ , which are identical or different from one another, denote a straight-chain or branched C _1-30 alkyl group or a phenyl group, in particular -CH ₃
• - The groups R ² , which are identical or different, R ¹ or a group -C _c H _{2 c} -O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) bR ⁵ or a group C _c H _{2 c} -O- (C ₄ H ₈ O) _a -R ⁵ with the proviso that at least one of the radicals R ^{2 is} a group -C _c H _{2 c} -O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -R ⁵ or a group C _c H _{2 c} -O- (C ₄ H ₈ O) _a -R ⁵ ,
• The groups R ³ and R ⁴ , which are identical or different, denote a straight-chain or branched C _1-12 -alkyl group and preferably methyl,
• - The groups R ⁵ , which are identical or different from one another, selected from a hydrogen atom, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a straight chain gene or branched alkoxy group with 1 to 6 carbon atoms, a straight-chain or branched acyl group with 2 to 40 carbon atoms, -SO ₃ M, a C _1-6 aminoalkoxy group optionally substituted on the amino group, a C _2-6 optionally substituted on the amino group aminoacyl, -NHCH ₂ CH ₂ COOM, -N (CH ₂ CH ₂ COOM) _2, an unsubstituted or substituted at the amino group and aminoalkyl group on the alkyl group, a C _{2-3 0} -Carboxyacylgruppe, an optionally substituted with one or two aminoalkyl groups substituted Phosphono group, -CO (CH ₂ ) _d COOM, -COCHR ₇ (CH ₂ ) _d COOM, -NHCO (CH ₂ ) _d OH, -NH ₃ Y or a phosphate group,
• The groups M, which are identical or different from one another, denote hydrogen, Na, K, Li, NH ₄ or an organic amine,
• - R _{7 is} hydrogen or SO ₃ M,
• - d is in the range from 1 to 10,
• - m is in the range from 0 to 20,
• - n is in the range from 0 to 500,
• O is in the range from 0 to 20,
• P is in the range from 1 to 50,
• A is in the range from 0 to 50,
• B is in the range from 0 to 50,
• - a + b means at least 2,
• - c is in the range from 0 to 4,
• - x is in the range from 1 to 100, and
• Y is a monovalent inorganic or organic anion,

with the proviso that n is above 12 if the silicone means the formula (II) with R ₅ = hydrogen.

• – R₂ und R'₂, die identisch oder unterschiedlich sind, ein einwertiges kohlenwasserstoffhaltiges Radikal darstellen,
• – n eine ganze Zahl von 2 bis 4 ist,
• – q eine Zahl von mindestens 4 ist, vorzugsweise zwischen 4 und 200 und insbesondere zwischen 4 und 100,
• – r eine Zahl von mindestens 4 ist, vorzugsweise zwischen 4 und 200 und insbesondere zwischen 5 und 100,
• – s eine Zahl von mindestens 4 ist, vorzugsweise zwischen 4 und 1000 und insbesondere zwischen 5 und 300,
• – Z eine zweiwertige organische Gruppe darstellt, die über eine Kohlenstoff-Silicium-Bindung an das benachbarte Siliciumatom und über ein Sauerstoffatom an einen Polyoxyalkylenblock gebunden ist,
• – das mittlere Molekulargewicht jedes Siloxanblocks zwischen 400 und ca. 10.000 liegt, das jedes Polyoxyalkylenblocks zwischen ca. 300 und ca. 10.000 liegt,
• – die Siloxanblöcke ca. 10 bis ca. 95 Gew.-% des Blockcopolymers darstellen,
• – das zahlenmittlere Molekulargewicht des Blockcopolymers zwischen 2.500 bis 1.000.000 und vorzugsweise zwischen 3.000 und 200.000 und insbesondere zwischen 6.000 und 100.000 liegen kann.

The polyalkoxylated silicones according to the invention can also be selected from the silicones of the following formula M: ([Z (R ₂ SiO) _q R ' ₂ SiZO] [(C _n H _{2 n} O) _r ]) _S (V) in the

• R ₂ and R ' ₂ , which are identical or different, represent a monovalent hydrocarbon radical,
• - n is an integer from 2 to 4,
• Q is a number of at least 4, preferably between 4 and 200 and in particular between 4 and 100,
• R is a number of at least 4, preferably between 4 and 200 and in particular between 5 and 100,
• S is a number of at least 4, preferably between 4 and 1000 and in particular between 5 and 300,
• Z represents a divalent organic group which is bonded to the adjacent silicon atom via a carbon-silicon bond and to a polyoxyalkylene block via an oxygen atom,
• The average molecular weight of each siloxane block is between 400 and approximately 10,000, that of each polyoxyalkylene block is between approximately 300 and approximately 10,000,
• The siloxane blocks represent about 10 to about 95% by weight of the block copolymer,
• - The number average molecular weight of the block copolymer can be between 2,500 to 1,000,000 and preferably between 3,000 and 200,000 and in particular between 6,000 and 100,000.

R ₂ and R ' ₂ are preferably selected from the group containing the straight-chain or branched alkyl radicals, such as, for example, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl radicals , the aryl radicals, for example the phenyl, naphthyl radicals, the aralkyl radicals or alkylaryl radicals, for example the benzyl, the phenylethyl radicals, the tolyl, xylyl radicals.

Z is preferably -R '' -, -R '' - CO-, -R '' - NHCO-, -R '' - NH-CO-NH-R '' -, -R '''- OCONH-R "" -NHCO-, where R "is a divalent, straight-chain or branched alkylene group having 1 to 6 carbon atoms, such as ethylene, propylene or butylene, straight-chain or branched, and R""is a divalent alkylene group or a divalent arylene group like -C ₆ H ₄ -, -C ₆ H ₄ -C ₆ H ₄ -, -C ₆ H ₄ CH ₂ -C ₆ H ₄ -, -C ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ - is.

More preferably, Z represents a divalent alkylene radical, especially the radical -C ₃ H ₆ or the radical C ₄ H ₆ , straight-chain or branched.

The preparation of the block copolymers used in the context of this invention is described in the European application EP 0 492 657 A1 described, the teaching of which is contained in this description.

Products of this type are sold, for example, under the name SILICONFLUID FZ-2172 OSI company marketed.

The silicones according to the invention can be found in Form watery solutions or optionally in the form of aqueous Dispersions or emulsions are present.

Silicones containing polyurethanes (B-5)

• a) mindestens einem Polysiloxanen,
• b) mindestens einem Polyesterdiol,
• c) mindestens einer Verbindung mit einem Molekulargewicht im Bereich von 56 bis 300, die zwei aktive Wasserstoffatome pro Molekül enthält,
• d) mindestens einer Verbindung, die zwei aktive Wasserstoffatome und mindestens eine anionogene bzw. anionische Gruppe pro Molekül aufweist,
• e) mindestens einem Diisocyanat,

oder die Salze davon, wobei das Polyurethan keine von einem primären oder sekundären Amin, welches eine ionogene bzw. ionische Gruppe aufweist, stammende Einheit enthält.Silicones containing polyurethanes can also be used as silicones. Water-soluble or water-dispersible polyurethanes are particularly suitable

• a) at least one polysiloxane,
• b) at least one polyester diol,
• c) at least one compound with a molecular weight in the range from 56 to 300, which contains two active hydrogen atoms per molecule,
• d) at least one compound which has two active hydrogen atoms and at least one anionogenic or anionic group per molecule,
• e) at least one diisocyanate,

or the salts thereof, wherein the polyurethane contains no unit derived from a primary or secondary amine which has an ionogenic or ionic group.

Component a) is concerned is preferably a polymer with a number average molecular weight in the range of about 400 to 4,000, preferably 500 to 4,000, in particular 600 to 3,000.

worin
R¹ und R² unabhängig voneinander für C₁- bis C₄-Alkyl, Benzyl oder Phenyl stehen,
X und Y unabhängig voneinander für OH oder NHR³ stehen, wobei R³ für Wasserstoff, C₁- bis C₆-Alkyl oder C₅- bis C₈-Cycloalkyl steht,
m und n unabhängig voneinander für 2 bis 8 stehen,
p für 3 bis 50 steht.The polysiloxanes a) are preferably a compound of the formula

wherein
R ¹ and R ² independently of one another are C ₁ -C ₄ -alkyl, benzyl or phenyl,
X and Y independently of one another represent OH or NHR ³ , where R ^{3 represents} hydrogen, C ₁ -C ₆ -alkyl or C ₅ -C ₈ -cycloalkyl,
m and n independently of one another represent 2 to 8,
p represents 3 to 50.

Suitable alkyl radicals are e.g. B. methyl, Ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl etc. Suitable cycloalkyl radicals are z. B. cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc.

Preferably R ¹ and R ^{2 are} both methyl.

Useful polyester diols b) have a number average molecular weight in the range of about 400 to 5,000, preferably 500 to 3,000, in particular 600 to 2,000.

worin R¹⁰ für H oder CH₃ steht und R¹¹ für C₁-C_{1 8}-Alkyl (insbesondere C₁-C₁₂- oder C₁-C₈-Alkyl) steht, die eine Molmasse von bis zu etwa 3000 aufweisen. Derartige Diole sind auf übliche Weise herstellbar und im Handel erhältlich (Tegomer^TM-Typen MD, BD und OD der Fa. Goldschmidt).Suitable polyester diols are all those which are customarily used for the production of polyurethanes, in particular those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc., aliphatic dicarboxylic acids, such as adipic acid or succinic acid etc., and cycloaliphatic dicarboxylic acids such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. Particularly suitable diols are aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, and also poly (meth) acrylate diols of the formula

wherein R ¹⁰ is H or CH ₃ and R ¹¹ (in particular C ₁ -C ₁₂ - or C ₁ -C ₈ -alkyl) -C _{1 1 8} alkyl C is having a molecular weight of up to about 3000th Such diols can be prepared in the usual way and are commercially available (Tegomer ^™ types MD, BD and OD from Goldschmidt).

Polyester diols are preferred Basis of aromatic and aliphatic dicarboxylic acids and aliphatic diols, especially those in which the aromatic dicarboxylic acid 10 to 95 mol%, in particular 40 to 90 mol% and preferably 50 to 85 mol% of the total dicarboxylic acid content (Rest of aliphatic dicarboxylic acids) from makes.

Particularly preferred polyester diols are the reaction products of phthalic acid / diethylene glycol, isophthalic acid / 1,4-butanediol, isophthalic acid / adipic acid / 1,6-hexanediol, 5-NaSO ₃ isophthalic acid / phthalic acid / adipic acid / 1,6-hexanediol, adipic acid / ethylene glycol, Isophthalic acid / adipic acid / neopentyl glycol, isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane and 5-NaSO ₃ - isophthalic acid / isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane.

Component c) is concerned are preferably diols, diamines, amino alcohols, and mixtures thereof. The molecular weight of these compounds is preferably one Range from about 56 to 280. If desired can up to 3 mol% of the compounds mentioned by triols or triamines to be replaced. The resulting polyurethanes are essentially uncrosslinked.

Preferred as component c) Diols used. Useful diols are e.g. B. ethylene glycol, propylene glycol, Butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, Tetra-, penta- or hexaethylene glycol and mixtures thereof. Prefers neopentyl glycol and / or cyclohexanedimethylol are used.

Suitable amino alcohols are e.g. B. 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl-4-aminopentan-2-ol etc.

Suitable diamines are e.g. B. ethylenediamine, Propylene diamine, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane as well a, w-Diaminopolyether by amination of polyalkylene oxides can be produced with ammonia.

Suitable compounds d), the two active hydrogen atoms and at least one anionogenic or anionic Group per molecule have z. B. Compounds with carboxylate and / or sulfonate groups. As Component d) are dimethylolpropanoic acid and mixtures which contain dimethylolpropanoic acid, particularly preferred.

Compounds of the formulas can also be used as component d) HN ₂ (CH ₂ ) _n -NH- (CH ₂ ) _m -COO ^- M ⁺ H ₂ N (CH ₂ ) _n -NH- (CH ₂ ) _m -SO ₃ ^- M ⁺
wherein m and n independently of one another represent an integer from 1 to 8, in particular 1 to 6, and M represents Li, Na or K. Mixtures which have dimethylolpropanoic acid and up to 3% by weight, based on the total amount of components a) to e), of at least one compound of the abovementioned formulas are preferably used as component d).

Component e) is concerned usual aliphatic, cycloaliphatic and / or aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer mixtures, 1,5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexyl methane diisocyanate and mixtures thereof, in particular isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. If desired, can up to 3 mol% of the compounds mentioned are replaced by triisocyanates his.

• – 0,5 bis 40 Gew%, bevorzugt 2 bis 30 Gew%, wenigstens eines Polysiloxans a),
• – 1 bis 45 Gew%, bevorzugt 2 bis 35 Gew%, wenigstens eines Polyesterdiols b),
• – 0,3 bis 15 Gew%, bevorzugt 0,5 bis 12 Gew%, wenigstens einer Komponente c),
• – 5 bis 25 Gew%, bevorzugt 8 bis 20 Gew%, wenigstens einer Komponente d),
• – 25 bis 60 Gew%, bevorzugt 35 bis 53 Gew%, wenigstens einer Komponente e).

Compounds are preferably used as the silicone-containing polyurethanes (B-5)

• 0.5 to 40% by weight, preferably 2 to 30% by weight, of at least one polysiloxane a),
• 1 to 45% by weight, preferably 2 to 35% by weight, of at least one polyester diol b),
• 0.3 to 15% by weight, preferably 0.5 to 12% by weight, of at least one component c),
• 5 to 25% by weight, preferably 8 to 20% by weight, of at least one component d),
• 25 to 60% by weight, preferably 35 to 53% by weight, of at least one component e).

• – 0,2 bis 20 Gew%, bevorzugt 0,5 bis 15 Gew%, insbesondere 1 bis 10 Gew%, wenigstens eines Polysiloxans a),
• – 10 bis 45 Gew%, bevorzugt 15 bis 40 Gew%, wenigstens eines Polyesterdiols b),
• – 0,3 bis 15 Gew%, bevorzugt 0,5 bis 12 Gew%, wenigstens einer Komponente c),
• – 5 bis 25 Gew%, bevorzugt 8 bis 20 Gew%, wenigstens einer Komponente d),
• – 25 bis 60 Gew%, bevorzugt 35 bis 53 Gew%, wenigstens einer Komponente e).

It is preferably a silicone-containing polyurethane

• 0.2 to 20% by weight, preferably 0.5 to 15% by weight, in particular 1 to 10% by weight, of at least one polysiloxane a),
• 10 to 45% by weight, preferably 15 to 40% by weight, of at least one polyester diol b),
• 0.3 to 15% by weight, preferably 0.5 to 12% by weight, of at least one component c),
• 5 to 25% by weight, preferably 8 to 20% by weight, of at least one component d),
• 25 to 60% by weight, preferably 35 to 53% by weight, of at least one component e).

The silicone-containing polyurethanes are produced by reacting the compounds of components a), b), c) and d) with component e). The temperature is in a range from approximately 60 to 140 ° C., preferably approximately 70 to 100 ° C. The reaction can be carried out without a solvent or in a suitable inert solvent or solvent mixture. Suitable solvents are aprotic polar solvents, e.g. B. tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, dimethylformamide and preferably ketones such as acetone and methyl ethyl ketone. The reaction is preferably carried out under an inert gas atmosphere, such as. B. under nitrogen. The components are used in amounts such that the ratio of the NCO equivalent of the compounds of component e) to the equivalent of the active hydrogen atom of the components ten a), b), c) and d) in a range from about 0.8: 1 to 1.25: 1, preferably 0.85: 1 to 1.2: 1, in particular 1.05: 1 to 1 , 15: 1, lies. If the resulting polyurethanes still have free isocyanate groups, these are finally inactivated by adding amines, preferably amino alcohols. Suitable amino alcohols are those described above as component c), preferably 2-amino-2-methyl-1-propanol.

The polyurethanes containing acid groups can through partial or complete Neutralization with a base in a water-soluble or water-dispersible Form to be transferred.

The salts of the polyurethanes obtained generally have better water solubility or dispersibility in water than the non-neutralized polyurethanes. Alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amines can be used as the base for the neutralization of the polyurethanes. Suitable amines are e.g. B. C ₁ -C ₆ alkylamines, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine, C ₁ -C ₆ alkyldiethyanolamines, preferably methyl- or ethyldiethanolamine and di -C ₁ -C ₆ alkylethanolamines. 2-Amino-2-methyl-1-propanol, diethylaminopropylamine and triisopropanolamine have proven particularly suitable for use in hair treatment compositions for neutralizing the polyurethanes containing acid groups. The neutralization of the polyurethanes containing acid groups can also be carried out with the aid of mixtures of several bases, for. B. Mixtures of sodium hydroxide solution and triisopropanolamine. Depending on the application, the neutralization can be partially z. B. 20 to 40% or completely, ie 100%.

Used in the manufacture of polyurethanes used a water-miscible organic solvent, so can this be followed by usual methods known to those skilled in the art, e.g. B. by distillation at reduced Pressure to be removed. Before removing the solvent, the polyurethane additionally Water can be added. After replacing the solvent with water, you get one Solution or Dispersion of the polymer from which, if desired, the polymer in the usual Way can be obtained, e.g. B. by spray drying.

The silicone-containing polyurethanes (B-5) have K values (measured according to E. Fikentscher, Cellulose-Chemie 13 (1932), pp. 58-64, on a 1% solution in N-methylpyrrolidone) in a range from 15 to 90, preferably 20 to 60. Your glass transition temperature is generally at least 0 ° C, preferably at least 20 ° C, particularly preferably at least 25 ° C. and especially at least 30 ° C.

Are used as silicone-containing polyurethanes (B-5) Polyurethanes with units derived from polysiloxanes of the formula I. used, is that related to the solids content of the silicone-containing polyurethanes Proportion of siloxane groups in general about 0.05 to 20% by weight, preferably about 0.05 to 15% by weight, in particular 0.05 to 10% by weight.

Particularly preferred as silicones are polyalkoxylated silicones (B-4).

• i) ethylenisch ungesättige Monomere (A-1) in Gegenwart von ungesättigten Polyalkylenglykolvinylethern (A-2) polymerisiert
• ii) das so erhaltene Polymerisat mit Silikonen bei einer Temperatur von größer gleich 30 °C mischt.

Another object of the present invention relates to a method for producing polymeric products, characterized in that

• i) ethylenically unsaturated monomers (A-1) polymerized in the presence of unsaturated polyalkylene glycol vinyl ethers (A-2)
• ii) the polymer thus obtained is mixed with silicones at a temperature greater than or equal to 30 ° C.

i) Preparation of polymers (A)

The preparation of the polymers (A) can according to usual conventional synthetic methods of polymerization. For example this solution polymerization, Emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without limiting the methods that can be used. In solution polymerization can Water, usual organic solvents or the unsaturated Polyalkylene glycol vinyl ether (A-2) itself can be used as a solvent.

The usual ones known to the person skilled in the art can be used as regulators Compounds such as sulfur compounds (e.g. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan) as well as tribromochloromethane or other compounds that regulate the molecular weight of the polymers obtained are used become. It can optionally also silicone compounds containing thiol groups become. Silicone-free controllers are preferably used.

In one embodiment of the invention, additional crosslinking monomers are used in the preparation of the polymers (A). Crosslinking monomers which can be used are compounds having at least two ethylenically unsaturated double bonds, for example esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, for example vinyl ether or allyl ether. Also suitable are straight-chain or branched, linear or cyclic aliphatic or aromatic hydrocarbons which have at least two double bonds which are not conjugated to the aliphatic hydrocarbons allowed to. Also suitable are amides of acrylic and methacrylic acid and N-allylamines of at least divalent amines such as (1,2-diaminoethane, 1,3-diaminopropane). Furthermore, triallylamine or corresponding ammonium salts, N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes. Other suitable crosslinkers are divinyl dioxane, tetraallylsilane or tetravinylsilane.

Crosslinkers are particularly preferred for example methylenebisacrylamide, triallylamine and triallylammonium salts, Divinylimidazole, N, N'-divinylethylene urea, Reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been implemented.

The monomers (A-1) according to the invention can, if they contain ionizable groups, before or after the polymerization, partially or completely with acids or bases are neutralized, for example, water solubility adjust or dispersibility to a desired level.

As a neutralizing agent for acid groups supporting monomers can for example mineral bases such as sodium carbonate, alkali hydroxides as well Ammonia, organic bases such as amino alcohols, especially 2-amino-2-methyl-1-propanol, Monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, Tri [(2-hydroxy) 1-propyl] amine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol and Diamines such as lysine can be used.

As a neutralizing agent for cationisable Monomers bearing groups can for example mineral acids like hydrochloric acid, sulfuric acid or phosphoric acid, as well as organic acids such as carboxylic acids, lactic acid, citric acid or others are used.

The monomers (A-1) of the polymers (A) can from 50 to 99.9% by weight, preferably 70 to 99% by weight, particularly preferably Make up 85 to 98 wt .-%, in particular 80 to 97 wt .-%.

The monomers (A-2, unsaturated polyalkylene glycol vinyl ether) are usually in amounts from 0.1 to 50, preferably from 0.5 to 20, particularly preferably from 2 to 15% by weight in the polymer (A) contain.

In a preferred embodiment of the invention, at least 2 monomers (a1 and a2) used. Polymers (A) which are particularly preferred by polymerization of monomer (a1) tert-butyl acrylate and monomer (a2) methacrylic acid available are. Are the ethylenically unsaturated monomers (A-1) as Combination of two monomers (a1 and a2) used, it has proven to be advantageous, 49.5 to 99% by weight (a1) and 0.5 to 40 % By weight (a2).

• (a1) 49,5 bis 99 Gew. % (Meth)acrylat, insbesondere tert.-Butylacrylat
• (a2) 0,5 bis 40 Gew. % eines weiteren (Meth)acrylats, insbesondere Methacrylsäure
• (b) 0,5 bis 20 Gew. % eines ungesättigten Polyalkylenglykolethers (A-2)

In a particularly preferred embodiment, the polymer (A) used is a polymer which can be obtained by free-radical polymerization of a monomer mixture from

• (a1) 49.5 to 99% by weight of (meth) acrylate, in particular tert-butyl acrylate
• (a2) 0.5 to 40% by weight of a further (meth) acrylate, in particular methacrylic acid
• (b) 0.5 to 20% by weight of an unsaturated polyalkylene glycol ether (A-2)

• (a1) 49,5 bis 99 Gew. % (Meth)acrylat, insbesondere tert.-Butylacrylat
• (a2) 0,5 bis 40 Gew. % eines weiteren (Meth)acrylats, insbesondere Methacrylsäure
• (c) 0,5 bis 20 Gew. % eines ungesättigten Polyalkylenglykolethers (A-2) der folgenden Formel H₂C=CH-C_cH_2c-O(C₂H₄O)_a(C₃H₆)_b-R⁵ – wobei R⁵=H, CH₃, – a im Bereich von 0 bis 50 liegt, – b im Bereich von 0 bis 50 liegt, – a + b größer 0 ist, – c 0, 1, 2, 3 oder 4 ist

In a particularly preferred embodiment, the polymer (A) used is a polymer which can be obtained by free-radical polymerization of a monomer mixture from

• (a1) 49.5 to 99% by weight of (meth) acrylate, in particular tert-butyl acrylate
• (a2) 0.5 to 40% by weight of a further (meth) acrylate, in particular methacrylic acid
• (c) 0.5 to 20% by weight of an unsaturated polyalkylene glycol ether (A-2) of the following formula H ₂ C = CH-C _c H _2c -O (C ₂ H ₄ O) _a (C ₃ H ₆ ) _b -R ⁵ - where R ⁵ = H, CH ₃ , - a is in the range from 0 to 50, - b is in the range from 0 to 50, - a + b is greater than 0, - c is 0, 1, 2, 3 or 4

The polymers (A) preferably have a K value (according to Fickentscher, Cellulosechemie, Vol. 13, pp. 58-64 (1932) at 250 ° C 0.1 5% in 0.5 molar saline solution) from 30 to 50 on, preferably 37 to 41.

Particularly suitable polymers (A) are those that are water soluble are or whose water dispersibility is so great that they are in a solvent mixture Water: ethanol = 20:80 (% by volume:% by volume) in an amount of more than 0.1 g / l, preferably more than 0.2 g / l, are soluble.

For the purposes of the invention, "water-dispersible" means polymers meant that in contact with the water within 24 hours a fluid form that without optical aids with the eye no fixed Particles can be recognized. To check whether a polymer is water-dispersible, 100 mg of the polymer in Form a 100 mm thick film in 100 ml of water (20 ° C) and on a commercially available shaking for 24 Shaken for hours. If after shaking no more solid particles can be seen, but the fluid is cloudy, the polymer is water-dispersible; without cloudiness it is said to be water soluble.

In the polymerization of the monomers (A-1) and (A-2) can optionally other polymers such as homopolymers and copolymers of ethylenically unsaturated Monomers as well as polyamides, polyurethanes or polyesters. The polyamides, polyurethanes, polyesters are preferably ionic modified, e.g. with carboxylate or sulfonate groups.

ii) mixing of polymers (A) with silicones (B)

The polymeric products according to the invention are in the simplest case available by mixing components (A) and (B). It is essential to the invention that the temperature when mixing is greater than or equal 30 ° C, in particular greater or equal Is 40 ° C.

In a particularly preferred embodiment According to the invention, the polymeric products according to the invention are produced, by (A) and (B) at temperatures greater than or equal to 50 ° C., in particular greater than or equal to 60 ° C, especially preferably greater than or equal to 70 ° C mixes.

It has proven to be beneficial mixing for perform at least 30 minutes, especially at least 60 minutes.

All are suitable for mixing Apparatus known to those skilled in the art. Mixing can be done under gassing with inert gas, e.g. Nitrogen fumigation carried out become.

In a preferred embodiment 99.5 to 70 wt .-%, in particular 99 to 85 wt .-% (A) and 0.5 to 30 wt .-%, in particular 1 to 15 wt .-% (B) used.

The polymeric products according to the invention are suitable are particularly suitable for use in cosmetic preparations, especially in hair cosmetic preparations.

Another subject of the present The invention therefore relates to the use of the polymeric products in cosmetic preparations.

For example, the polymers of the invention Products used in cosmetic products for cleaning the skin. Such cosmetic cleaning agents are selected from bar soaps, such as toilet soaps, Core soaps, transparent soaps, luxury soaps, deodorant soaps, cream soaps, Baby soaps, skin protection soaps, abrasive soaps and syndets, liquid soaps, like pasty Soaps, soft soaps and washing pastes, and liquid washing, showering and bathing preparations, such as washing lotions, shower baths and gels, foam baths, oil baths and Scrub preparations.

The polymers according to the invention are preferred Products in cosmetic products for the care and protection of the skin, used in nail care products and in preparations for decorative cosmetics.

Use is particularly preferred in skin care products, intimate hygiene products, foot care products, deodorants, Sunscreen agents, repellents, shaving agents, hair removal agents, Anti-acne agents, make-up, mascara, lipsticks, eye shadows, kohl pencils, Eyeliners, blushes, powders and eyebrow pencils.

The skin care products are in particular as W / O or O / W skin creams, day and night creams, eye creams, Face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, Vitamin creams, skin lotions, skin care lotions and moisturizing lotions in front.

In the cosmetic preparations can the polymers of the invention Por products have special effects. You can use it for moisturizing, among other things and conditioning the skin and improving skin feel. By adding the polymers according to the invention Products in certain formulations can make a significant improvement skin tolerance can be achieved.

The polymeric products according to the invention are in the skin cosmetic preparations in a proportion of about 0.001 up to 20% by weight, preferably 0.01 to 10% by weight, very particularly preferably 0.1 to 5 wt .-%, based on the total weight of the agent.

Depending on the application, the agents according to the invention in a form suitable for skin care, e.g. as a cream, foam, Gel, pen, powder, mousse, milk or lotion can be applied.

The skin cosmetic preparations can in addition to the dispersions of the invention and suitable solvents still common in cosmetics Additions, such as emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, Light stabilizers, bleaches, colorants, tinting agents, tanning agents (e.g. dihydroxyacetone), collagen, protein hydrolyzates, stabilizers, pH regulators, dyes, salts, thickeners, gelling agents, consistency agents, Silicones, humectants, moisturizers and other common ones Contain additives.

Particularly suitable solvents are to name water and low monoalcohols or polyols with 1 to 6 carbon atoms or mixtures thereof; preferred mono alcohols or polyols are ethanol, i-propanol, propylene glycol, glycerin and sorbitol.

Other common additives may include fatty substances such as mineral and synthetic oils such as paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils such as sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes , Fatty acids, fatty acid esters, such as triglycerides of C ₆ -C ₃₀ fatty acids, wax esters, such as jojoba oil, fatty alcohols, Vaseline, hydrogenated lanolin and acetylated lanolin. Mixtures of the same can of course also be used.

usual Thickeners in such formulations are cross-linked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, agar agar, alginates or tylosen, carboxymethyl cellulose or hydroxycarboxymethyl cellulose, Fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and Polyvinylpyrrolidone.

The polymers according to the invention can be used Products also with conventional ones Mix polymers if special properties are set should.

Are suitable as conventional polymers for example anionic, cationic, amphoteric and neutral polymers.

Examples of anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer ^TM 100P), copolymers of ethyl acrylate and methacrylic acid (e.g. Luvimer ^TM MAE), copolymers of N-tert-butyl-acrylamide, ethyl acrylate, acrylic acid (Ultrahold ^TM 8 , strong), copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (e.g. Luviset ^TM brands), maleic anhydride copolymers, optionally reacted with alcohols, anionic polysiloxanes, e.g. carboxy-functional, copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid (e.g. Luviskol ^TM VBM), Copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C ₄ -C ₃₀ alkyl esters of meth (acrylic acid), C ₄ -C ₃₀ alkyl vinyl esters, C ₄ -C ₃₀ alkyl vinyl ethers and hyaluronic acid. Luviset PUR, Luviflex ^TM Silk.

Other suitable polymers are cationic polymers with the name Polyquaternium according to INCI, for example copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^TM FC, Luviquat ^TM HM, Luviquat ^TM MS, Luviquat ^TM Care, Luviquat ^TM Hold, INCI Polyquaternium-16, -44, -46), copolymers of acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), cationic starch derivatives (INCI: Starch Hydroxypropytrimonium Chloride, Corn Starch Modified), cationic guar derivatives (INCI: Hydroxypropyl Guimino Hydroxide) , cationic sunflower oil derivatives (INCI: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride), copolymers made of N-vinypyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Polyquaternium-11), copolymers made of acrylic acid, acrylamide and methacrylamidopropyltrimonium chloride (Polyquium 32-quaternium chloride) (Polyquium 32-quaternium-53) and other.

Neutral are also other polymers Suitable polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, copolymers of N-vinypyrrolidone / dimethylaminopropylacrylamide or methacrylamide, copolymers of N-vinylpyrrolidone and alkyl acrylate or methacrylate monomers with alkyl chains from C1 to C18, graft copolymers from polyvinyl alcohol to polyalkylene glycols such as e.g. Kollicoat IR (BASF), graft copolymers of other vinyl monomers on polyalkylene glycols, Polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, Polyethyleneimines and their salts, polyvinylamines and their salts, Cellulose derivatives, chitosan, polyaspartic acid salts and derivatives.

For setting certain properties can the preparations additionally also conditioning substances based on silicone compounds contain. Suitable silicone compounds are, for example, polyalkylsiloxanes, Polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins, Dimethicone, Dimethicone Derivatives or Dimethicone Copolyols (CTFA) and amino functional silicone compounds such as Amodimethicone (CTFA).

The polymeric products according to the invention are used in cosmetic preparations, the manufacture of the usual familiar to the expert Rules.

Such formulations are advantageously in the form of emulsions, preferably as water-in-oil (W / O) or oil-in-water (O / W) emulsions in front. However, it is also possible and possibly advantageous according to the invention to choose other types of wording, for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous Ointments or ointment bases etc.

The production more useful according to the invention Emulsions are carried out according to known methods.

The emulsions contain in addition to the polymers according to the invention Products usual Constituents, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, Lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.

The selection of the emulsion type-specific additions and the preparation of suitable emulsions is described, for example in Schrader, Basics and Recipes for Cosmetics, Hüthig Book Verlag, Heidelberg, 2nd edition, 1989, third part, whereupon herewith expressly Reference is made.

So can be used according to the invention Skin cream e.g. present as a W / O emulsion. Such an emulsion contains an aqueous Phase, using a suitable emulsifier system in an oil or fat phase is emulsified.

The concentration of the emulsifier system in this type of emulsion is about 4 and 35% by weight, based on the total weight of the emulsion; the fat phase makes up about 20 and 60% by weight and the aqueous phases about 20 and 70% by weight, each based on the total weight of the emulsion. The emulsifiers are those which are usually used in this type of emulsion. They are chosen, for example: C _{1 2} -C ₁₈ sorbitan Fettsäureestern; Esters of hydroxystearic acid and C _{1 2} -C ₃₀ fatty alcohols; Mono- and diesters of C _{1 2-C18} fatty acids and glycerol or polyglycerol; Condensates of ethylene oxide and propylene glycols; oxypropylenated / oxyethylenated C ₁ -C ₂₀ fatty alcohols _2; polycyclic alcohols such as sterols; high molecular weight aliphatic alcohols such as lanolin; Mixtures of oxypropylene / polyglycerolated alcohols and magnesium isostearate; Succinic esters of polyoxyethylenated or polyoxypropylenated fatty alcohols; and mixtures of magnesium, calcium, lithium, zinc or aluminum lanolate and hydrogenated lanolin or lanolin alcohol.

Suitable fat components, which The fat phase of the emulsions may include hydrocarbon oils, such as Paraffin oil, purCellin, Perhydroscal and solutions microcrystalline waxes in these oils; animal or vegetable oils, such as Sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil, Sesame oil, Olive oil, jojoba oil, Shea oil, Hoplostethus oil; mineral oils, their start of distillation under atmospheric pressure at about 250 ° C and their Distillation end point at 410 ° C lies, such as vaseline oil; Ester more saturated or more unsaturated fatty acids, such as alkyl myristates, e.g. i-propyl, butyl or cetyl myristate, hexadecyl stearate, Ethyl or i-propyl palmitate, octanoic or decanoic acid triglycerides and cetylricinoleate.

The fat phase can also be silicone oils soluble in other oils, such as Dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and contain fatty alcohols.

To favor the retention of oils, you can also use waxes, e.g. Carnauba wax, candella wax, Beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.

Generally, these are water-in-oil emulsions Made so that the fat phase and emulsifier are added to the batch container become. One warms up this at a temperature of 70 to 75 ° C, then gives the oil-soluble Ingredients and adds with stirring Add water that was previously heated to the same temperature and in which the water-soluble Ingredients previously solved Has; you stir until an emulsion of the desired Has delicacy then cool them down to room temperature, possibly less stirred becomes.

Furthermore, a care emulsion according to the invention present as an O / W emulsion. Such an emulsion usually contains an oil phase, Emulsifiers that affect the oil phase stabilize in the water phase, and an aqueous phase, usually is thickened.

• – Alkohole, Diole oder Polyole sowie deren Ether, vorzugsweise Ethanol, Isopropanol, Propylenglycol, Glycerin, Ethylenglycolmonoethylether;
• – übliche Verdickungsmittel bzw. Gelbildner, wie z.B. vernetzte Polyacrylsäuren und deren Derivate, Polysaccharide wie Xanthan Gum oder Alginate, Carboxymethylcellulose oder Hydroxycarboxymethylcellulose, Fettalkohole, Polyvinylalkohol und Polyvinylpyrrolidon.

The aqueous phase of the O / W emulsion of the preparations according to the invention optionally contains

• - Alcohols, diols or polyols and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol monoethyl ether;
• - Common thickeners or gelling agents, such as cross-linked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum or alginates, carboxymethyl cellulose or hydroxy carboxymethyl cellulose, fatty alcohols, polyvinyl alcohol and polyvinyl pyrrolidone.

• – Ester aus gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten C₃-C_{3 0}-Alkancarbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten C₃-C₃₀-Alkoholen, aus aromatischen Carbonsäuren und gesättigten und/oder ungesättigten, verzweigten und/oder unverzweigten C₃-C_{3 0}-Alkoholen, beispielhaft Isopropylmyristat, Isopropylstearat, Hexyldecylstearat, Oleyloleat; außerdem synthetische, halbsynthetische und natürliche Gemische solcher Ester, wie Jojobaöl;
• – verzweigte und/oder unverzweigte Kohlenwasserstoffe und -wachse;
• – Silikonöle wie Cyclomethicon, Dimethylpolysiloxan, Diethylpolysiloxan, Octamethylcyclotetrasiloxan sowie Mischungen daraus;
• – Dialkylether;
• – Mineralöle und Mineralwachse;
• – Triglyceride gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter C₈-C₂₄-Alkancarbonsäuren; sie können ausgewählt werden aus synthetischen, halbsynthetischen oder natürlichen Ölen, wie Olivenöl, Palmöl, Mandelöl oder Mischungen.

The oil phase contains common oil components in cosmetics, such as:

• - esters of saturated and / or unsaturated, branched and / or unbranched C ₃ -C _{3 0} alkanecarboxylic acids and saturated and / or unsaturated, branched and / or unbranched _C3-C30 alcohols, and saturated aromatic carboxylic acids and / or unsaturated, branched and / or unbranched C ₃ -C _{3 0} alcohols, for example isopropyl myristate, isopropyl stearate, hexyldecyl stearate, oleyl oleate; also synthetic, semi-synthetic and natural mixtures of such esters as jojoba oil;
• - branched and / or unbranched hydrocarbons and waxes;
• - silicone oils such as cyclomethicone, dimethylpolysiloxane, diethylpolysiloxane, octamethylcyclotetrasiloxane and mixtures thereof;
• - dialkyl ether;
• - mineral oils and mineral waxes;
• - Triglycerides of saturated and / or unsaturated, branched and / or unbranched C ₈ -C ₂₄ alkane carboxylic acids; they can be selected from synthetic, semi-synthetic or natural oils, such as olive oil, palm oil, almond oil or mixtures.

Preferred emulsifiers are O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified Glycerides.

The production can be done by melting the oil phase at approx. 80 ° C respectively; the water soluble Ingredients are in hot Water dissolved, slowly and with stirring to the oil phase added; homogenized and stirred cold.

The polymeric products according to the invention are suitable are also suitable for use in washing and shower gel formulations as well Bath preparations.

Such formulations contain in addition the polymers of the invention Products usually anionic Surfactants as a base surfactant and amphoteric and nonionic surfactants as cosurfactants, as well as lipids, perfume oils, dyes, organic acids, Preservatives and antioxidants as well as thickeners / gelling agents, Skin conditioners and humectants.

In the washing, showering and bathing preparations can all common in personal cleansers anionic, neutral, amphoteric or cationic surfactants used be used.

The formulations contain 2 to 50% by weight of surfactants, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight.

Suitable anionic surfactants are for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, Alkyl glycol alkoxylates, acyl taurates, acyl isethionates, alkyl phosphates, Alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units have in the molecule.

For example, sodium lauryl sulfate is suitable, Ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, Sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, Sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

Suitable amphoteric surfactants are for example alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, Alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, Alkyl amphodiacetates, or dipropionates.

For example, cocodimethylsulfopropyl betaine, Lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate be used.

Examples of nonionic surfactants are suitable the reaction products of aliphatic alcohols or Alkylphenols with 6 to 20 carbon atoms in the alkyl chain that are linear or can be branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles to one mole of alcohol. Furthermore, alkylamine oxides, Mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, Alkyl polyglycosides or sorbitan ether esters are suitable.

In addition, the washing, shower and Bath products usual cationic Contain surfactants such as quaternary ammonium compounds, for example Cetyltrimethylammonium chloride or bromide (INCI cetrimonium chloride or bromides), hydroxyethyl cetyldimonium phosphate (INCI Quatemium-44), INCI Cocotrimonium Methosulfate, INCI Quaternium-52.

In addition, other customary cationic ones Polymers are used, e.g. Copolymers of acrylamide and Dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), cationic starch derivatives (INCI: Starch Hydroxypropytrimonium Chloride, Corn Starch Modified), cationic guar derivatives (INCI: hydroxypropyl guar hydroxypropyltrimonium Chlorides), cationic sunflower oil derivatives (INCI: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride), copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole (Polyquaternium-16, -44, -46), Copolymers of N-vinypyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (polyquaternium-11), copolymers of acrylic acid, acrylamide and methacrylamidopropyltrimonium chloride (Polyquaternium-53), Polyquaternium-32, Polyquaternium-28 and others.

Furthermore, the washing and shower gel formulations and bath preparations Thickeners, e.g. Cooking Salt, PEG-55, Propylene Glycol Oleate, PEG-120 Methyl glucose dioleates and others, as well as preservatives, contain other active substances and auxiliary substances and water.

In a preferred embodiment The end result is the polymeric products in hair cosmetic preparations used.

Hair cosmetic preparations include in particular styling agents and / or conditioning agents in hair cosmetics Preparations such as hair treatments, hair foams (English Mousses), (hair) gels or hair sprays, hair lotions, hair rinses, hair shampoos, hair emulsions, Top fluids, leveling agents for perms, hair dye and bleach, "hot oil treatment" preparations, Conditioners, setting lotions or hair sprays. Depending on the area of application can the hair cosmetic preparations as (aerosol) spray, (aerosol) foam, Gel, gel spray, cream, lotion or wax can be applied.

• a) 0,05 bis 20 Gew.-% des polymeren Produkts
• b) 20 bis 99,95 Gew.-% Wasser und/oder Alkohol
• c) 0 bis 79,5 Gew.-% weitere Bestandteile

In a preferred embodiment, the hair cosmetic formulations according to the invention contain

• a) 0.05 to 20 wt .-% of the polymeric product
• b) 20 to 99.95 wt .-% water and / or alcohol
• c) 0 to 79.5% by weight of further constituents

Under alcohol are all common in cosmetics Understand alcohols, e.g. Ethanol, isopropanol, n-propanol.

Among other components are the ones common in cosmetics additions to understand, for example blowing agents, defoamers, surfactants Connections, i.e. Surfactants, emulsifiers, foaming agents and solubilizers. The surfactants used Connections can be anionic, cationic, amphoteric or neutral. Other common ingredients can further be e.g. Preservatives, perfume oils, plasticizers, effect substances, Opacifiers, Active ingredients, antioxidants, peroxide decomposers, UV filters, care substances such as panthenol, collagen, vitamins, protein hydrolyzates, alpha and beta hydroxycarboxylic acids, protein hydrolyzates, Stabilizers, pH regulators, Dyes, pigments, viscosity regulators, Gelling agents, salts, humectants, refatting agents, complexing agents and more usual Additives.

Furthermore, this includes all in cosmetics well-known styling and conditioner polymers, which in combination with the polymers according to the invention can be used if very special properties are to be set.

Anionic polymers, for example, are suitable as conventional hair cosmetic polymers. Such anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes (Luviset ^TM PUR) and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer ^TM 100P), copolymers of N-tert-butyl acrylamide, ethyl acrylate, acrylic acid (for example Ultrahold ^TM 8, Strong), copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (e.g. Luviset ^TM brands, INCI: VA / Crotonates Copolymer), maleic anhydride copolymers, possibly reacted with alcohols, anionic polysiloxanes, e.g. carboxy-functional, copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid (e.g. Luviskol ^TM VBM).

The group of polymers suitable for combination with the polymeric products according to the invention also includes, for example, Balance CR or 0/55 (National Starch; acrylate copolymer), Balance 47 (National Starch; octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer), Aquaflex ^™ FX 64 (ISP; Isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer), Aquaflex ^TM SF-40 (ISP / National Starch; VP / Vinyl Caprolactam / DMAPA acrylate copolymer), Allianz ^TM LT-120 (ISP / Rohm &Haas; acrylate / C1-2 succinate / hydroxyacrylate- copolymer), Aquarez ^{T M} HS (Eastman, polyester-1), Diaformer ^TM Z-400 (Clariant; methacryloylethylbetaine / methacrylate copolymer), Diaformer ^TM Z-711 or Z-712 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer ), Omnirez ^TM 2000 (ISP; monoethyl ester of poly (methyl vinyl ether / maleic acid in ethanol), Amphomer ^TM HC or Resyn XP or Resyn 28-4961 (National Starch; acrylate / octylacrylamide copolymer), Amphomer ^TM 28-4910 (National Starch; octylacrylamide / acrylate / butyl aminoethyl methacrylate copolymer), Advantage ^™ HC 37 (ISP; Terpolymer made of vinyl caprolactam / vinyl pynolidone / dimethylaminoethyl methacrylate), Advantage brands (ISP), Acudyne 258 (Rohm &Haas; acrylate / hydroxyester acrylate copolymer), Luviset ^TM PUR (BASF, Polyurethane-1), Luviflex ^TM Silk (BASF, PEG / PPG- 25/25 Dimethicone / Acrylates Copolymer), Eastman ^TM AQ48 (Eastman), Styleze 2000 (ISP; VP / Acrylates / Lauryl Methacrylate Copolymer), Styleze CC-10 (ISP; VP / DMAPA Acrylates Copolymer), Styleze W-20 (ISP ), Fixomer A-30 (Ondeo Nalco; Methacrylic Acid / Sodium Acrylamidomethyl Propane Sulfonate Copolymer), Fixate G-100 (Noveon; AMP-Acrylates / Allyl Methacrylate Copolymer).

Are very particularly preferred as anionic polymers Acrylates with an acid number greater than or equal to 120 and copolymers from t-butyl acrylate, ethyl acrylate, methacrylic acid.

Other suitable hair cosmetic polymers are cationic polymers with the name Polyquaternium according to INCI, for example copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^TM FC, Luviquat ^TM HM, Luviquat ^TM MS, Luviquat ^TM Care, INCI: Polyquaternium-16, Polyquaternium-44) , copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^{T M} PQ 11, INCI: Polyquaternium-11), copolymers of N-vinyl caprolactam, N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^TM Hold, INCI: Polyquaternium-46); Copolymers of acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), cationic starch derivatives (INCI: Starch Hydroxypropytrimonium Chloride, Corn Starch Modified), cationic guard derivatives (INCI: Hydroxypropyl Guar Hydroxypropyltriumium- Sonnenoxid) Derivatives (INCI: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride), copolymers of acrylic acid, acrylamide and methacrylamidopropyltrimonium chloride (INCI: Polyquaternium-53), Polyquaternium-32, Polyquaternium-28 and others.

Neutral hair polymers are also suitable as further hair cosmetic polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpynolidone and vinyl acetate and / or vinyl propionate, copolymers of N-vinypyrrolidone / dimethylaminopropylacrylamide or methacrylamide, copolymers of N-vinylpynolidone and alkyl acrylate mono- or methacrylic mono- or methacrylamide C18, graft copolymers of polyvinyl alcohol on polyalkylene glycols, such as, for example, Kollicoat IR (BASF), graft copolymers of other vinyl monomers on polyalkylene glycols, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, polyparasine derivatives, cellulosic acid derivatives, cellulose silicate derivatives rivate.

For setting certain properties can the preparations additionally also conditioning substances based on silicone compounds contain. Suitable silicone compounds are, for example, polyalkylsiloxanes, Polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins, fluorinated alkyl silicones, dimethicones, dimethicone derivatives or Dimethicone copolyols (CTFA) and amino functional silicone compounds like Amodimethicone (CTFA).

The polymers according to the invention are suitable especially as a setting agent in hair styling preparations, especially hair sprays (aerosol sprays and pump sprays without propellant) and hair foams (Aerosol foams and pump foams without propellant).

• a) 0,1 bis 10 Gew.-% des erfindungsgemäßen polymeren Produkts
• b) 20 bis 99,9 Gew.-% Wasser und/oder Alkohol
• c) 0 bis 70 Gew.-% eines Treibmittel
• d) 0 bis 20 Gew.-% weitere Bestandteile

In a preferred embodiment, these preparations contain

• a) 0.1 to 10 wt .-% of the polymeric product according to the invention
• b) 20 to 99.9% by weight of water and / or alcohol
• c) 0 to 70 wt .-% of a blowing agent
• d) 0 to 20% by weight of further constituents

Blowing agents are those for hair sprays or aerosol foams commonly used Propellant. Mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air.

• a) 0,1 bis 10 Gew.-% des erfindungsgemäßen polymeren Produkts
• b) 55 bis 99,8 Gew.-% Wasser und/oder Alkohol
• c) 5 bis 20 Gew.-% eines Treibmittel
• d) 0,1 bis 5 Gew.-% eines Emulgators
• e) 0 bis 10 Gew.-% weitere Bestandteile

A formulation according to the invention for aerosol hair foams contains

• a) 0.1 to 10 wt .-% of the polymeric product according to the invention
• b) 55 to 99.8% by weight of water and / or alcohol
• c) 5 to 20 wt .-% of a blowing agent
• d) 0.1 to 5% by weight of an emulsifier
• e) 0 to 10 wt .-% other ingredients

As emulsifiers, all of them can usually be found in hair foams emulsifiers used are used. Suitable emulsifiers can be non-ionic, cationic or anionic or amphoteric.

Examples of nonionic emulsifiers (INCI nomenclature) are Laurethe, e.g. Laureth-4; Cetethe, e.g. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, e.g. Cetheareth-25, Polyglycolfettsäureglyceride, hydroxylated lecithin, lactyl esters of fatty acids, alkyl polyglycosides.

Examples of cationic emulsifiers are or bromide (INCI cetrimonium chloride or bromide), hydroxyethyl cetyldimonium phosphate (INCI Quaternium-44), INCI Cocotrimonium Methosulfate, INCI Quaternium-52, Quaternium-1 to x (INCI).

Anionic emulsifiers can for example selected are selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, alkylglycol alkoxylates, Acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, Alkyl ether carboxylates, alpha olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferred Have 1 to 3 ethylene oxide units in the molecule.

• a) 0,1 bis 10 Gew.-% der erfindungsgemäßen polymeren Produkte
• b) 60 bis 99,85 Gew.-% Wasser und/oder Alkohol
• c) 0,05 bis 10 Gew. % eines Gelbildners
• d) 0 bis 20 Gew.-% weitere Bestandteile

A preparation suitable according to the invention for styling gels can be composed, for example, as follows:

• a) 0.1 to 10 wt .-% of the polymeric products according to the invention
• b) 60 to 99.85 wt .-% water and / or alcohol
• c) 0.05 to 10% by weight of a gel former
• d) 0 to 20% by weight of further constituents

All of the usual cosmetics can be used as gel formers Gel formers are used. These include slightly cross-linked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, e.g. Xanthum Rubber, caprylic / capric triglycerides, sodium acrylates copolymer, Polyquaternium-32 (and) Paraffinum Liquidum (INCI), Sodium Acrylates Copolymer (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-10 Allyl Ether Acrylates Copolymer, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, Polyquaternium 37 (and) Propylene Glycole Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium-44.

The polymeric products according to the invention can be used in cosmetic preparations are used as conditioning agents. Examples are for Rinse-often and leave-on conditioner preparations.

• a) 0,05 bis 10 Gew.-% der erfindungsgemäßen polymeren Produkte
• b) 25 bis 94,95 Gew.-% Wasser
• c) 5 – 50 Gew.-% Tenside
• c) 0 – 5 Gew.-% eines weiteren Konditioniermittels
• d) 0 – 10 Gew.-% weitere kosmetische Bestandteile

The polymeric products according to the invention can also be used in shampoo formulations as setting and / or conditioning agents. Polymers with a cationic charge are particularly suitable as conditioning agents. Preferred shampoo formulations included

• a) 0.05 to 10 wt .-% of the polymeric products according to the invention
• b) 25 to 94.95 wt .-% water
• c) 5-50% by weight of surfactants
• c) 0-5% by weight of a further conditioning agent
• d) 0-10% by weight of further cosmetic ingredients

In the shampoo formulations everyone can usually in shampoos anionic, neutral, amphoteric or cationic surfactants used be used.

Suitable anionic surfactants are for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, Acyl taurates, acyl isethionates, alkyl glycol alkoxylates, alkyl phosphates, Alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule exhibit.

For example, sodium lauryl sulfate is suitable, Ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, Sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, Sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

Suitable amphoteric surfactants are for example alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, Alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, Alkyl amphodiacetates or dipropionates.

For example, cocodimethylsulfopropyl betaine, Lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate be used.

Examples of nonionic surfactants are suitable the reaction products of aliphatic alcohols or Alkylphenols with 6 to 20 carbon atoms in the alkyl chain that are linear or can be branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles to one mole of alcohol. Furthermore, alkylamine oxides, Mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, Alkyl polyglycosides or sorbitan ether esters are suitable.

In addition, the shampoo formulations can be conventional cationic Contain surfactants such as quaternary ammonium compounds, for example Cetyltrimethylammonium chloride or bromide (INCI cetrimonium chloride or bromides), hydroxyethyl cetyldimonium phosphate (INCI Quaternium-44), INCI Cocotrimonium Methosulfate, INCI Quaternium-52.

In order to achieve certain effects, customary conditioning agents can be used in combination with the polymers according to the invention in the shampoo formulations. These include, for example, cationic polymers with the name Polyquaternium according to INCI, for example copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^TM FC, Luviquat ^TM HM, Luviquat ^TM MS, Luviquat ^TM Care, INCI: Polyquaternium-16, Polyquaternium-44), copolymers from N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^TM PQ 11, INCI: Polyquaternium-11), copolymers of N-vinylcaprolactam N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^TM Hold, INCI: 46; polyquaternium; Copolymers of acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10). Furthermore, cationic starch derivatives (INCI: Starch Hydroxypropytrimonium Chloride, Corn Starch Modified), cationic guar derivatives (INCI: Hydroxypropyl Guar Hydroxypropyltrimonium Chloride), cationic sunflower oil derivatives (INCI: Sunflowerseedamidopropyl Hydroxyethyldimonium Chloride), copolymers of acrylic acid, acrylamide and INCI: acrylamide, methylene chloride, INC -53), Polyquaternium-32, Polyquaternium-28 and others can be used. Protein hydrolyzates can also be used, and conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins. Other suitable silicone compounds are dimethicones, dimethicone derivatives or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).

Examples

Preparation example

example 1

a) (2206/188) manufacture of the polymer (A)

The template was heated to 78 ° C. under nitrogen gas and left at 78 ° C. for 15 minutes. Feed 1 was then metered in within 2 hours, and feed 2 was metered in over 2.5 hours. Polymerization was then continued for 2 hours and feed 3 was then metered in over 15 minutes. Template: 250 g Ethanol, cosm. P 63 g luriol A 11 R 100 g Inlet 1 7.5 g Inlet 2 Inlet 1: 120 g Ethanol, cosm. 562 g tert-butyl 188 g methacrylic acid Inlet 2: 200 g Ethanol, cosm. 3 g tert-butyl perpivalate (75%) Inlet 3: 240 g Ethanol, cosm. 3 g tert-butyl perpivalate (75%)

The polymer A thus obtained had a solids content of 51.3%, a K value (1% in ethanol) of 39.1 and an acid number (mg KOH / g) of 80.1.

b) mixing (A) with Silicone (B)

In a 2 liter four-necked flask 243.7 g of the polymer obtained according to a) and 13.84 g of polyalkoxylated Silicon (Belsil DMC 6031, Wacker) with nitrogen gas 78 ° C one Stirred for an hour.

The product so obtained had one Fixed content of 55.9%, a K value (1% in ethanol) of 37.1 and an acid number (mg KOH / g) of 81.6.

Comparative Example 1

For Comparative example 1 was carried out analogously to example 1 (polymer A and silicone B). However, the two components were at room temperature (20 ° C) Stirred for 1 hour.

Application properties

a) Stiffness measurement (Flexural rigidity)

For measuring the bending stiffness become 3.0% by weight solutions of the polymeric products according to Example 1 and the comparative example 1 manufactured. The bending stiffness is measured on 5 to 10 strands of hair (approx. 3 g and 24 cm in length) at 20 ° C and 65% rel. Moisture carried out. The weighed, dry strands of hair are in the 3% polymer solution immersed, with three immersion and removal one even distribution is ensured. The excess film forming solution will stripped between thumb and forefinger and the strands of hair become subsequently by expressing between filter paper carefully expressed. After that, the strands shaped by hand so that they have a round cross-section. At 20 ° C and 65% rel. Moisture gets over Dried at night in the climate room.

The exams were in a climate room at 20 ° C and 65% rel. Moisture carried out using a tension / pressure tester. The strand of hair becomes symmetrical on two cylindrical rollers of the sample holder placed. Right in the middle is now rounded off from above with a Stamp the streak Bent 40 mm (breaking of the polymer film). The necessary Power is with a load cell (50 N) measured and given in Newtons.

b) Measurement of curl retention

To measure curl retention 1.8% by weight solutions of the polymeric products according to Example 1 and the comparative example 1 manufactured. The measurement of the curl retention was carried out as follows: The washed, dry strands of hair were 15 minutes at about 40 ° C in 50% ethanol (absolute ethanol / distilled water 1: 1). With The excess liquid was squeezed out of the thumb and forefinger the strand of hair wrapped around a plexiglass tube. Subsequently, the strands of hair were left overnight at 65 to 70 ° C dried. After 15 minutes at room temperature, the hair was unwound. Approximately 5 g of hair spray (from a distance of approx. 20 cm) were sprayed on the curl was turned. After that, she was lying at room temperature for 1 hour dried.

L = Länge der Haare (15,5 cm)
Lo = Länge der Haare nach dem Trocknen
Lt = Länge der Haare nach KlimabehandlungThe curl was hung at one end and the curl length (LO) measured. The curl was placed in a climatic chamber (25 ° C, 90% relative humidity) and its length (Lt) measured after 15, 30, 60 and 90 minutes, as well as after 2, 3, 4, 5 and 24 hours. The test was carried out on at least 5 strands of hair.

L = length of hair (15.5 cm)
Lo = length of hair after drying
Lt = length of hair after climatic treatment

Table 1 shows the flexural strength values and curl retention of Example 1 and Comparative Example 1.

Table 1: Flexural rigidity in cN (3% by weight WS in absolute ethanol; 20 ° C and 65% relative humidity) and curl retention (%)

Haarsprays mit Propan/Butan 3.5 bar bzw. Propan/Butan 3.5 bar mit DME-Zusatz

Pumpsprays

Haarspray-Formulierung auf Basis Dimethylether 1,00 Gew.-% Luviskol K30^TM (BASF) 2,92 Gew.-% polymeres Produkt gemäß Beispiel 1 0,92 Gew.-% 2-Amino-2-methylpropanol 0,10 Gew.-% Diisobutyladipate (Bsp. Crodanol DiBA von Croda Oleochemicals 0,05 Gew.-% Isodecan 0,10 Gew.-% Parfümöl 0,05 Gew. % D-Panthenol USPT (BASF) 14,78 Gew.-% Wasser entmineralisiert 36,08 Gew.-% Ethanol 40,00 Gew.-% Dimethylether Haarsprayformulierungen auf Basis iso-Butan und n-Pentan

Glanzspray 2,00 % Luviset CA66^TM (BASF) 2,00 % polymeres Produkt gemäß Beispiel 1 0,46 % 2-Amino-2-methylpropanol 1,00 % DOW Corning 556 (Dow Corning) 0,10 % Niacinamid 0,20 % D-Panthenol USP^TM (BASF) 14,20 % n-Pentan 35,90 % n-Butan 44,14 % Ethanol Haarspay VOC 80 mit HFC 152A 2,00 % Luviset CA66^TM(BASF) 4,80 % Polymeres Produkt gemäß Beispiel 1 0,79 % 2-Amino-2-methylpropanol 56,60 % Ethanol 15,81 % Prapellant 152a (Bsp. Dymel 152a von DuPont) 20,00 % Dimethylether Haarspray VOC 55 mit Vitaminen 4,80 % Polymeres Produkt gemäß Beispiel 1 3, 33 % Luviset P. U. R. ^TM 0,57 % 2-Amino-2-methylpropanol 0,10 % Niacinamid (Hoffmann-La Roche) 0,10 % Panthenol USP^TM(BASF) 38,83 % Wasser entmineralisiert 12,27 % Ethanol 40,00 % Dimethylether Sonnenschutz-Pumpspray fürs Haar 2,00 % polymeres Produkt gemäß Beispiel 1 0,23 % 2-Amino-2-methylpropanol 2,00 % Uvinul MS 40^TM (BASF) (Benzophenone-4) 95,77 % Ethanol Hair Repair 1,00 % Luviskol K30^TM (BASF) 4,00 % Polymeres Produkt gemäß Beispiel 1 0,48 % 2-Amino-2-methylpropanol 0,20 % Hydrolized Wheat Protein (Bsp. Cropesol WT von Croda, Inc.) 0,50 % D-Panthenol USP^TM (BASF) 5,00 % 1,2-Propylen GlycolUSP^TM (BASF) 10,00 % Ethanol 78,82 % Wasser entmineralisiert Shining Gel für Haare mit UV-Schutz

Maskara (Wimperntusche)

Shampoo-Formulierung 1,50 % Polymeres Produkt gemäß Beispiel 1 0,17 % 2-Amino-methylpropanol 0,50 % Luviskol K30^TM (BASF) 10,00 % Tego-Betaine L7 40,00 % Texapone NSO 0,10 % Euxyl K100 2,00 % NaCl 45,73 % Wasser Shampoo-Formulierung mit Luviquat Care^TM 1,80 % Polymeres Produkt gemäß Beispiel 1 0,21 % 2-Amino-methylpropanol 0,20 % Luviskol K30^TM (BASF) 7,70 % Luviquat Care^TM (BASF) 10,00 % Tego-Betaine L7 40,00 % Texapone NSO 0,10 % Euxyl K 100 2,00 % NaCl 37,99 % Wasser Klarlack 15,0 % Nitrocellulose 7,0 % Polymeres Produkt gemäß Beispiel 1 2,4 % Campher 4,5 % Palatinol A 7,0 % Isopropanol 8,0 % Methylacetat 8,0 % Ethylacetat 14,0 % Essigsäureisopropylester 34,1 % Butylacetat Klarlack ohne Nitrocellulose 23,0 % Polymeres Produkt gemäß Beispiel 1 7,0 % Ketjenflex MH 2,4 % Campher 4,5 % Palatinol A 8,0 % Methylacetat 8,0 % Ethylacetat 14,0 % Essigsäureisopropylester 33,1 % Butylacetat VOC 55 Haarspray 21,50 % Wasser 35,00 % Alkohol SD 40-B 0,95 % Aminomethyl Propanol 8,00 % Polymeres Produkt gemäß Beispiel 1 0,20 % D,L Panthenol 0,10 % Uvinul^TM MC 80 (Octyl Methoxycinnamate) 0,10 % Masil^TM SF 19 (Dimethicone Copolyol) 15,00 % Dimethyl Ether 20,00 % Hydrofluorocarbon 152a VOC 55 Haarspray 34,10 % Wasser 52,00 % Alkohol SD 40-B 0,50 % Aminomethyl Propanol 9,00 % LuvisetTM P.U.R. Polyurethane-1) 4,00 % Polymeres Produkt gemäß Beispiel 1 2,00 % D,L Panthenol 0,10 % Uvinul^TM MC 80 (Octyl Methoxycinnamate) 0,10 % Masil^TM SF 19 (Dimethicone Copolyol) As can be seen from the table, the bending stiffness of the polymeric product according to the invention is significantly higher than that of the comparative example while maintaining the curl retention properties. formulation Examples

Hair sprays with propane / butane 3.5 bar or propane / butane 3.5 bar with DME addition

pump sprays

Hairspray formulation based on dimethyl ether 1.00% by weight Luviskol K30 ^TM (BASF) 2.92% by weight polymeric product according to Example 1 0.92% by weight 2-amino-2-methylpropanol 0.10% by weight Diisobutyl adipates (e.g. Crodanol DiBA from Croda Oleochemicals 0.05% by weight isododecane 0.10% by weight perfume oil 0.05% by weight D-Panthenol USPT (BASF) 14.78% by weight Demineralized water 36.08% by weight ethanol 40.00% by weight dimethyl ether Hair spray formulations based on isobutane and n-pentane

shine spray 2.00% Luviset CA66 ^TM (BASF) 2.00% polymeric product according to Example 1 0.46% 2-amino-2-methylpropanol 1.00% DOW Corning 556 (Dow Corning) 0.10% niacinamide 0.20% D-Panthenol USP ^TM (BASF) 14.20% n-pentane 35.90% n-butane 44.14% ethanol Hairspray VOC 80 with HFC 152A 2.00% Luviset CA66 ^TM (BASF) 4.80% Polymeric product according to example 1 0.79% 2-amino-2-methylpropanol 56.60% ethanol 15.81% Prapellant 152a (e.g. Dymel 152a from DuPont) 20.00% dimethyl ether Hair spray VOC 55 with vitamins 4.80% Polymeric product according to example 1 3.33% Luviset PUR ^TM 0.57% 2-amino-2-methylpropanol 0.10% Niacinamide (Hoffmann-La Roche) 0.10% Panthenol USP ^TM (BASF) 38.83% Demineralized water 12.27% ethanol 40.00% dimethyl ether Sun protection pump spray for the hair 2.00% polymeric product according to Example 1 0.23% 2-amino-2-methylpropanol 2.00% Uvinul MS 40 ^TM (BASF) (Benzophenone-4) 95.77% ethanol Hair repair 1.00% Luviskol K30 ^TM (BASF) 4.00% Polymeric product according to example 1 0.48% 2-amino-2-methylpropanol 0.20% Hydrolized Wheat Protein (e.g. Cropesol WT from Croda, Inc.) 0.50% D-Panthenol USP ^TM (BASF) 5.00% 1,2-Propylene GlycolUSP ^TM (BASF) 10.00% ethanol 78.82% Demineralized water Shining gel for hair with UV protection

Mascara (mascara)

Shampoo formulation 1.50% Polymeric product according to example 1 0.17% 2-amino-methylpropanol 0.50% Luviskol K30 ^TM (BASF) 10.00% Tego-Betaine L7 40.00% Texapone NSO 0.10% Euxyl K100 2.00% NaCl 45.73% water Shampoo formulation with Luviquat Care ^TM 1.80% Polymeric product according to example 1 0.21% 2-amino-methylpropanol 0.20% Luviskol K30 ^TM (BASF) 7.70% Luviquat Care ^TM (BASF) 10.00% Tego-Betaine L7 40.00% Texapone NSO 0.10% Euxyl K 100 2.00% NaCl 37.99% water clearcoat 15.0% nitrocellulose 7.0% Polymeric product according to example 1 2.4% camphor 4.5% Palatinol A 7.0% isopropanol 8.0% methyl acetate 8.0% ethyl acetate 14.0% acetate 34.1% butyl Clear varnish without nitrocellulose 23.0% Polymeric product according to example 1 7.0% Ketjenflex MH 2.4% camphor 4.5% Palatinol A 8.0% methyl acetate 8.0% ethyl acetate 14.0% acetate 33.1% butyl VOC 55 hairspray 21.50% water 35.00% Alcohol SD 40-B 0.95% Aminomethyl propanol 8.00% Polymeric product according to example 1 0.20% D, L panthenol 0.10% Uvinul ^TM MC 80 (octyl methoxycinnamate) 0.10% Masil ^TM SF 19 (Dimethicone Copolyol) 15.00% Dimethyl ether 20.00% Hydrofluorocarbon 152a VOC 55 hairspray 34.10% water 52.00% Alcohol SD 40-B 0.50% Aminomethyl propanol 9.00% LuvisetTM PUR Polyurethane-1) 4.00% Polymeric product according to example 1 2.00% D, L panthenol 0.10% Uvinul ^TM MC 80 (octyl methoxycinnamate) 0.10% Masil ^TM SF 19 (Dimethicone Copolyol)

All percentages in the examples are, if not expressly mentioned differently Wt .-% - information.

Claims (14)

Process for the preparation of polymeric products, characterized in that i) polymerizing ethylenically unsaturated monomers (A-1) in the presence of unsaturated polyalkylene glycols (A-2) ii) the polymer thus obtained with silicones (B) at a temperature of greater than or equal to 30 ° C mixes. A method according to claim 1, characterized in that the silicones (B) selected are from the group consisting of (B-1) silicones with at least a quaternized or non-quaternized amine function, (B-2) Silicone resins, (B-3) silicone rubbers, (B-4) polyalkoxylated silicones and / or polyurethanes containing silicone (B-5). A method according to claim 1 and / or 2, characterized in that that mixing at a temperature greater than or equal to 40 ° C, in particular greater or equal 50 ° C. Polymer products available by mixing (A) Polymers that are available are by radical polymerization of (A-1) ethylenic unsaturated Monomers in the presence of (A-2) unsaturated polyalkylene glycols With (B) silicones at a temperature greater than or equal to 30 ° C Polymeric products according to claim 4, characterized in that the ethylenically unsaturated monomers (A-1) and the unsaturated polyalkylene glycols (A-2) in a ratio of 50 to 99.9% by weight (A-1) and 0.1 to 50 wt.% (A-2) are polymerized. Polymeric products according to claim 4 and / or 5, characterized characterized that 99.5 to 70 wt.% Polymer (A) and 0.5 to 30 wt .-% silicones (B) are used. Polymer products according to at least one of the aforementioned Expectations, characterized in that the silicones are selected from the group consisting of from (B-1) silicones with at least one quaternized or non-quaternized Amine function, (B-2) silicone resins, (B-3) silicone rubbers, (B-4) polyalkoxylated Silicones and / or silicone-containing polyurethanes (B-5). Polymeric products according to at least one of the preceding claims, characterized in that at least one compound of the following formula is used as monomer (A-1) XC (O) CR ⁷ = CHR ⁶ where X is selected from the group consisting of -OH, -OM, -0R ⁸⁸ , NH ₂ , -NHR ⁸ , N (R ⁸ ) ₂ M a cation is selected from the group consisting of: Na +, K +, Mg ++, Ca ++ , Zn ++, NH4 +, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; the radicals R ^{8 can be} identical or different selected from the group consisting of -H, C1-C40 linear or branched chain alkyl radicals, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl or ethoxypropyl , R ⁷ and R ^{6 are} independently selected from the group consisting of: -H, C ₁ -C ₈ linear or branched chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl. Polymer products according to at least one of the aforementioned Expectations, characterized in that the monomers (A-1) are selected from the group consisting of acrylic acid, methacrylic acid, ethyl acrylic acid, methyl acrylate, Ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate. Polymer products according to at least one of the aforementioned Expectations, characterized in that as monomers (A-1) at least 2 compounds are used, which are selected are from the group consisting of acrylic acid, methacrylic acid, ethyl acrylic acid, methyl acrylate, Ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate. Polymeric products according to at least one of the preceding claims, characterized in that compounds of the following formula are used as unsaturated polyalkylene glycols (A-2) H ₂ C = CH-C _c H _{2 c} -O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b -R ⁵ and or H ₂ C = CH- _c H _{2 c} -O- (C ₄ H ₈ O) _a -R ⁵ wherein - R ⁵ denotes -H, -CH = CH ₂ , - (CH ₂ ) ₅ -CH = CH- (CH ₂ ) _t -H, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, a straight-chain or branched alkoxy group with 1 to 6 carbon atoms, a straight-chain or branched acyl group with 2 to 40 carbon atoms, -SO ₃ M, a C _1-6 aminoacyl group optionally substituted on the amino group, -NHCH ₂ CH ₂ COOM, -N (CH ₂ CH ₂ COOM) ₂ , an aminoalkyl group optionally substituted on the amino group and on the alkyl group, a C _2-30 carboxyacyl group, a phosphono group optionally substituted with one or two substituted aminoalkyl groups, -CO (CH ₂ ) _d COOM, -COCHR ⁷ (CH ₂ ) _d COOM, -NHCO (CH ₂ ) _d OH, -NH ₂ Y or a phosphate group - the groups M, which are identical or different from each other, denote hydrogen, Na, K, Li, NH ₄ or an organic amine, - R ^{7 is} hydrogen or SO ₃ M, - d is in the range from 1 to 10, - s can be 0, 1 to 10 - t Can be 0.1 to 10 - a is in the range from 0 to 50, - b is in the range from 0 to 50, - a + b is greater than 0, - c is 0, 1, 2, 3 or 4, - Y means a monovalent inorganic or organic anion. Use of a polymeric product after at least one of the preceding claims in cosmetic preparations, especially in hair cosmetic Preparations. Use according to claim 12 as a strengthening agent and / or conditioning agents. Containing cosmetic preparation a) 0.05 up to 20% by weight of the polymeric product b) 20 to 99.95% by weight Water and / or alcohol c) 0 to 79.5% by weight of further constituents With the proviso that the shares add up to 100%.