EP1339383A2 - Cosmetic, pharmaceutical and dermatological products - Google Patents

Abstract

The invention relates to cosmetic, pharmaceutical and dermatological products, containing at least one copolymer which is obtained by radical copolymerisation of A) acryloyldimethyltaurine acid and/or acryloyldimethyltaurates, B) optionally, one or more additional olefinically unsaturated, non-cationic comonomers, C) optionally, one or more olefinically unsaturated, cationic comonomers, D) optionally, one or more components containing silicon, E) optionally, one or more components containing fluorine and F) optionally, one or more macromonomers, G) the copolymerisation taking place in the presence of at least one polymeric additive, H) provided that component A) is copolymerised with at least one component selected from one of the groups D) to G).

Description

description

Cosmetic, pharmaceutical and dermatological agents.

The present invention relates to cosmetic, pharmaceutical and dermatological compositions containing comb-shaped copolymers based on acryloyldimethyltauric acid.

Consumer wishes and the rheology of cosmetic products are closely linked. So will. e.g. the visual appearance of a cream or lotion is influenced by the viscosity. The sensory properties such as consistency or distributability determine the individual profile of a cosmetic product. The effectiveness of active substances (e.g. sun protection filters) and the storage stability of the formulation are closely related to the theological properties of the products.

In the cosmetic field, polyelectrolytes play a major role as thickeners and gel formers. The prior art is particularly thickeners based on poly (meth) acrylic acid and its water-soluble copolymers. The variety of possible structures and the associated diverse application possibilities are not least expressed in a large number of patents that have been registered worldwide since the mid-1970s. A major disadvantage of the thickeners based on poly (meth) acrylic acid is the strong pH dependence of the thickening performance. A sufficiently high viscosity is generally only built up when the pH of the formulation is set above pH 6, ie the poly (meth) acrylic acid is present in neutralized form. Furthermore, the corresponding agents are sensitive to UV radiation and shear and also impart a sticky feeling on the skin. The handling of such thickeners is also problematic. Since the thickeners are generally in acidic form, an additional neutralization step is required in the formulation. Novel thickeners based on cross-linked and neutralized polyacryloyldimethyl taurates were introduced to the market in the 1990s (EP-B-0 815 828, EP-B-0 815 844, EP-B-0 815 845 and EP-A-0 850 642) , Both in the form of the pre-neutralized homopolymer and as a corresponding copolymer ( ^® ARISTOFLEX AVC, CLARIANT GmbH), these thickeners are superior to the poly (meth) acrylate types in many respects. For example, acryloyldimethyl taurate-based thickener systems show excellent properties in pH ranges below pH 6, ie in a pH range in which it is no longer possible to work with conventional poly (meth) acrylate thickeners. High UV and shear stability, excellent viscoelastic properties, easy processing and a favorable toxicological profile of the main monomer make acryloyldimethyltaurate-based thickener systems modern, new representatives with high potential for the future.

Another thickener concept has been established on the market in recent years. The hydrophobic modification of the conventional poly (meth) acrylates gave access to polymers which have both thickening and emulsifying / dispersing properties. Examples of commercial hydrophobically modified poly (meth) acrylates are ^® PEMULEN TR-1 and TR-2 from BF Goodrich ^® and ACULYN 22 Rohm and Haas. Since these hydrophobically modified polymers are based on (meth) acrylic acid, they also have the disadvantages of poly (meth) acrylates mentioned above.

Surprisingly, it has now been found that a new class of

Comb polymers based on acryloyldimethyltauric acid (AMPS) - which are suitable as thickeners, consistency agents, emulsifiers, solubilizers, dispersants, lubricants, adhesives, conditioners and / or stabilizers - are ideally suited for the formulation of cosmetic, pharmaceutical and dermatological agents. The invention therefore relates to cosmetic, pharmaceutical and dermatological compositions comprising at least one copolymer which can be obtained by radical copolymerization of

A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates,

B) optionally one or more further olefinically unsaturated, non-cationic, optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, C) optionally one or more olefinically unsaturated cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol,

D) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization,

E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,

F) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each having at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number average molecular weight greater than or equal to 200 g / mol, the Macromonomers are not silicon-containing component D) or fluorine-containing component E), G) where the copolymerization is optionally carried out in the presence of at least one polymeric additive with number-average molecular weights of 200 g / mol to 10 ⁹ g / mol, H) with the proviso that component A) with at least one

Component selected from one of groups D) to G) is copolymerized. The copolymers according to the invention preferably have a molecular weight of 10 ³ g / mol to 10 ⁹ g / mol, particularly preferably 10 ⁴ to 10 ⁷ g / mol, particularly preferably 5 * 10 ⁴ to 5 * 10 ⁶ g / mol.

The Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinsäure (Acrylamidopropyl-2-methyl-2-sulfonic acid). The Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ and / or NH ⁺ salts are preferred. The monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, it being possible for the alkyl substituents of the amines, independently of one another, to be (C ₁ -C ₂₂ ) alkyl radicals or (C ₂ -CIO) hydroxyalkyl radicals. Furthermore, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above representatives are also within the meaning of the invention.

The degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.

Based on the total mass of the copolymers, the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.

All olefinically unsaturated, non-cationic monomers whose reaction parameters allow copolymerization with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media can be used as comonomers B). Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 30. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.

Preferred counterions are Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals the alkyl substituents of the amines can independently of one another be (C ₁ -C ₂₂ ) -alkyl radicals or (C ₂ -C ₁₀ ) -hydroxyalkyl radicals. In addition, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used. The degree of neutralization of the carboxylic acids can be between 0 and 100%.

Also preferred as comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N.N-dimethylamino methacrylate; Diethylamino-methyl; Acrylic and methacrylamido glycolic acid; 2- and 4-vinyl pyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; Vinyl chloride; stearyl; lauryl; vinylidene chloride; and / or tetrafluoroethylene. Also suitable as comonomers B) are inorganic acids and their salts and esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid and methallylsulfonic acid.

The proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.8% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight. Suitable comonomers C) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts. The resulting distribution of the cationic charges over the chains can be statistical, alternating, block-like or gradient-like. It should be pointed out that the cationic comonomers C) also include those which carry the cationic charge in the form of a betaine, zwitterionic or amphoteric structure. Comonomers C) in the sense of the invention are also amino-functionalized precursors which are converted into their corresponding quaternary (e.g. reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid) or amphomeric derivatives by polymer-analogous reactions can.

Are particularly preferred as comonomers C)

Diallyldimethylammonium chloride (DADMAC),

[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),

[2- (acryloyloxy) ethyl] trimethylammonium chloride,

[2-methacrylamidoethyl] trimethylammonium chloride, [2- (acrylamido) ethyl] trimethylammonium chloride,

N-methyl-2-vinyl pyridinium chloride

N-methyl-4-vinyl pyridinium chloride

dimethylaminoethyl

Dimethylaminopropyl methacrylamide, methacryloylethyl-N-oxide and / or

Methacryloylethyl betaine.

The proportion by weight of the comonomers C), based on the total mass of the copolymers, can be 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.

Suitable polymerizable, silicon-containing components D) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case are. The distribution of the individual silicone-containing monomers across the resulting polymer chains does not necessarily have to be statistical. The formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different silicone-containing representatives are also possible. The use of silicone-containing components with two or more polymerization-active groups leads to the formation of branched or cross-linked structures.

Preferred silicone-containing components are those of the formula (I).

R ¹ - Z- [(Si (R ³ R ⁴ ) -O-) _w - (Si (R ⁵ R ⁶ ) -O) χ -] - R ² (I)

R ^{1 represents} a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means. R ¹ preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic (CH ₂ = CH-CO-), methacrylic (CH ₂ = C [CH ₃ ] -CO-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical. A suitable chemical bridge Z is required to bind the silicone-containing polymer chain to the reactive end group R ¹ . Preferred bridges Z are -O-, - ((Ci - C ₅₀ ) alkylene) -, - ((C ₆ - C ₃₀ ) arylene) -, - ((C ₅ - C ₈ ) cycloalkylene) -, - ((Cι -C ₅ o) alkenylene) -, - (polypropylene oxide) _n -, - (polyethylene oxide) ₀ -, - (polypropylene oxide) n (polyethylene oxide) ₀ -, where n and o independently of one another represent numbers from 0 to 200 and the distribution of EO / PO units can be statistical or block-shaped. Also suitable as bridge groupings Z are - ((CΪ - C ₁₀ ) alkyl) - (Si (OCH ₃ ) ₂ ) - and - (Si (OCH ₃ ) ₂ ) -. The polymer middle part is represented by silicone-containing repeat units. The radicals R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another are -CH ₃ , -O-CH ₃ , -C ₆ H ₅ or -OC ₆ H ₅ .

The indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250. The distribution of the repeating units over the chain can not only be purely statistical, but can also be block-like, alternating or gradient-like.

R ² can symbolize on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (Ci - C ₅ o) carbon hydrogen radical (linear or branched) or -OH, -NH ₂ , -N (CH3) 2, -R ⁷ or for the

Structure unit [-ZR ¹ ] stand. The meaning of the two variables Z and R ¹ has already been explained. R ⁷ stands for further Si-containing groups. preferred

R ⁷ radicals are -O-Si (CH ₃ ) ₃ , -O-Si (Ph) ₃ , -O-Si (O-Si (CH ₃ ) ₃ ) 2CH ₃ ) and

-O-Si (O-Si (Ph) ₃ ) ₂ Ph).

If R ^{2 is} an element of the group [-ZR ¹ ], it is a bifunctional, monomers that crosslink the resulting

Polymer structures can be used.

Formula (l) describes not only vinylically functionalized, silicone-containing

Polymer species with a typical polymer distribution, but also defined

Discrete molecular weight compounds.

Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:

ethacryloxyproplydimethylsilyl endblocked polydimethylsiloxanes (f = 2 to 500)

Methacryloxypropyl endblocked polydimethylsiloxanes (f = 2 to 500 to)

Vinyldimethoxysilyl endblocked polydimethylsiloxanes (f = 2-500)

Based on the total mass of the copolymers, the content of silicon-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

Suitable polymerizable, fluorine-containing components E) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case. The distribution of the individual fluorine-containing monomers across the resulting polymer chains need not necessarily be statistical. The formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention. Combinations of two or more different fluorine-containing components E) are also possible, it being clear to the expert that monofunctional representatives lead to the formation of comb-shaped structures, whereas di-, tri- or polyfunctional components E) lead to at least partially crosslinked structures.

Preferred fluorine-containing components E) are those of the formula (II).

R ¹ -YC _r H2rCsF _2s CF ₃ (II)

R ^{1 represents} a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means. R is preferably vinyl, allyl, methallyl, methylvinyl, acrylic (CH ₂ = CH-CO-), methacrylic (CH ₂ = C [CH ₃ ] -CO-), crotonyl, Senecionyl, itaconyl, maleinyl, fumaryl or styryl radical, particularly preferably an acrylic and methacrylic radical.

A suitable chemical bridge Y is required to link the fluorine-containing group to the reactive end group R ¹ . Preferred bridges Y are -O-, _c (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ -CH (OH) -CH ₂ -O-, -O-SOz-O-, -OS (O) -O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH-, -N (CH ₃ ) -, -O- (C ₁ -C ₅ o) alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -O- (C ₅ -C ₈ ) cycloalkyl- O-, -O- (C ₁ -C ₅₀ ) alkenyl-O-, -O- (CH (CH ₃ ) -CH ₂ -O) n-, -O- (CH ₂ -CH ₂ -O) _n - and -O - ([CH-CH2-O] n- [CH ₂ -CH ₂ -O] m) o-, where n, m and o independently of one another are numbers from 0 to 200 and the distribution of the EO- and PO - Units can be statistical or block-shaped.

R and s are stoichiometric coefficients that independently represent numbers from 0 to 200.

Preferred fluorine-containing components E) according to formula (II) are

Perfluorohexylethanol methacrylate,

Perfluorhexoylpropanol methacrylate,

Perfluoroctyethanol methacrylate,

Perfluorooctylpropanol methacrylate, perfluorohexylethanolyl polyglycol ether methacrylate,

Perfluorohexoyl propanolyl poly [ethyl glycol co-propylene glycol ether acrylate,

Perfluoroctyethanolyl-poly [ethylene glycol-block co-propylene glycol] methacrylate,

Perfluoroctylpropanolyl-polypropylene-glycol ether methacrylate.

Based on the total mass of the copolymer, the content of fluorine-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

The macromonomers F) are at least simple olefinically functionalized polymers with one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers F) can also be used in the copolymerization. Both Macromonomers are polymeric structures that are composed of one or more repeating unit (s) and have a molecular weight distribution that is characteristic of polymers.

Preferred macromonomers F) are compounds of the formula (III).

R ¹ - Y - [(A) v - (B) _w - (C) _x - (D) _z ] - R ² (III)

R ¹ represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means. R ¹ preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic (CH ₂ = CH-CO-), methacrylic (CH ₂ = C [CH ₃ ] -CO-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical. A suitable bridging group Y is required to bind the polymer chain to the reactive end group. Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ - CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO ₂ -O-, -O-SO-O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -, particularly preferably -O-. The polymer middle part of the macromonomer is represented by the discrete repeat units A, B, C and D. preferred

Repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide. The indices v, w, x and z in formula (III) represent the stoichiometric

Coefficients relating to the repetition units A, B, C and D. v, w, x. And z are, independently of one another, 0 to 500, preferably 1 to 30, the sum of the four coefficients on average having to be ≥ 1. The distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.

R ² denotes a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrC _δ o) hydrocarbon residue, OH, -NH ₂ , -N (CH ₃ ) 2 or is identical to the structural unit [-YR ¹ ]. In the case of R ² equal to [-YR ¹ ], these are difunctional macromonomers which are suitable for crosslinking the copolymers.

Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).

R ₃ , R ₄ , R _δ and Rβ independently of one another denote hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrCsoJ hydrocarbon radicals.

R ₃ and R ₄ are preferably H or —CH ₃ , particularly preferably H; R ₅ is H or -CH ₃ ; and Rβ is equal to an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C ₃₀ ) hydrocarbon radical. v and w are again the stoichiometric coefficients relating to the ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w on average having to be> 1. The distribution of the EO and PO units over the macromonomer chain can be statistical, block-like, alternating or gradient-like. Y stands for the bridges mentioned above.

Further particularly preferred macromonomers F) have the following structure according to formula (IV):

Also particularly suitable as macromonomers F) are esters of (meth) acrylic acid with

(Cιo-Cι ₈ ) fatty alcohol polyglycol ethers with 8 EO units (Genapol ^® C-080) Cn-oxo alcohol polyglycol ethers with 8 EO units (Genapol ^® UD-080)

(Ci ₂ -Cι) fatty alcohol polyglycol ethers m 17 EO units (Genapol ^® LA-070) (Ci ₂ -Cι ₄ ) fatty alcohol polyglycol ethers m 1 11 EO units (Genapol ^® LA-110) (Ci ₆ - Cι ₈ ) fatty alcohol polyglycol ethers m 1 8 EO units (Genapol ^® T-080) (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ethers m 1 15 EO units (Genapol ^® T-150) (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ethers m ιt 11 EO units (Genapol ^® T-110) (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ethers with 120 EO units (Genapol ^® T-200) (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ethers with 25 EO units (Genapol ^® T-250) (-C ₈ -C ₂₂ ) fatty alcohol polyglycol ethers with 25 EO units and / or iso- (Ci ₆ -C ₈ ) fatty alcohol polyglycol ethers with 25 EO units The Genapol ^® types are products from Clariant, GmbH.

The molecular weight of the macromonomers F) is preferably 200 g / mol to 10 ⁶ g / mol, particularly preferably 150 to 10 ⁴ g / mol and particularly preferably 200 to 5000 g / mol.

Based on the total mass of the copolymers, suitable macromonomers up to 99.9% by weight can be used. The ranges 0.5 to 30% by weight and 70 to 99.5% by weight are preferably used. Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.

Preferred copolymers are those which can be obtained by copolymerizing at least components A), C) and D).

Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), C) and E).

Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), D) and F).

Also preferred as copolymers are those which can be obtained by copolymerizing at least components A) and F).

In a preferred embodiment, the copolymerization is carried out in the presence of at least one polymeric additive G), the additive G) being added to the polymerization medium in whole or in part in solution before the actual copolymerization. The use of several additives G) is also according to the invention. Crosslinked additives G) can also be used.

The additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium. During the actual polymerization step, additive G) has several functions. On the one hand, it prevents the formation of over-crosslinked polymer fractions in the copolymer being formed in the actual polymerization step and, on the other hand, the additive becomes G) attacked statistically by active radicals according to the generally known mechanism of graft copolymerization. As a result, depending on the additive G), more or less large amounts of it are incorporated into the copolymers. In addition, suitable additives G) have the property of changing the solution parameters of the copolymers which form during the radical polymerization reaction in such a way that the average molecular weights are shifted to higher values. Compared with analog copolymers which were produced without the addition of additives G), those which were produced with the addition of additives G) advantageously show a significantly higher viscosity in aqueous solution.

Preferred additives G) are homo- and copolymers soluble in water and / or alcohols, preferably in t-butanol. Copolymers are also to be understood as meaning those with more than two different types of monomers. Particularly preferred additives G) are homopolymers and copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.

Particularly preferred additives G) are polyvinylpyrrolidones (such as Luviskol K15 ^®, K20 ^® and K30 ^® from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.

The molecular weight of the additives G) is preferably 10 ² to 10 ⁷ g / mol, particularly preferably 0.5 * 10 ⁴ to 10 ⁶ g / mol.

The amount of polymeric additive G) used is, based on the total mass of the monomers to be polymerized during the copolymerization, preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight .-%. In a further preferred embodiment, the copolymers according to the invention are crosslinked, ie they contain comonomers with at least two polymerizable vinyl groups.

Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives. Trimethylolpropane triacrylate (TMPTA) is particularly preferred as the crosslinking agent. The proportion by weight of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.

All organic or inorganic solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which advantageously permit the formation of medium or high molecular weights. Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds.

The polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.

To initiate the polymerization, high-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators, such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, Methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators such as azodiisobutyronitrile (AIBN) can be used. Also suitable are inorganic peroxy compounds, such as (NH ₄ ) ₂ S ₂ O ₈ , K ₂ SO ₈ or H ₂ O ₂ , optionally in combination with reducing agents (e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or redox systems , which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.

All solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which allow the formation of high molecular weights. Water and lower, tertiary alcohols or hydrocarbons having 3 to 30 carbon atoms are preferably used. In a particularly preferred embodiment, t-butanol is used as the reaction medium. Mixtures of two or more representatives of the potential solvents described are of course also in accordance with the invention. This also includes emulsions of immiscible solvents (e.g. water / hydrocarbons). In principle, all types of reaction control which lead to the polymer structures according to the invention are suitable (solution polymerization, emulsion process, precipitation process, high-pressure process, suspension process, bulk polymerisation, gel polymerisation, etc.). Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol.

The following list shows 67 copolymers which are particularly suitable for the formulation of the agents according to the invention. The various copolymers No. 1 to No. 67 can be obtained according to the following production processes 1, 2, 3 and 4.

Procedure 1:

These polymers are in tert after the precipitation process. Butanol can be produced. The monomers were initially introduced into t-butanol, the reaction mixture was rendered inert and then the reaction after heating to 60 ° C. by addition of the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide) started. After the reaction has ended (2 hours), the polymers are isolated by suction extraction of the solvent and subsequent vacuum drying.

Procedure 2:

These polymers can be prepared in water using the gel polymerization process. The monomers are dissolved in water, the reaction mixture is rendered inert, and the reaction is then started after heating to 65 ° C. by adding suitable initiator or initiator systems (preferably Na ₂ S ₂ θ ₈ ). The polymer gels are then crushed and the polymers isolated after drying.

Process 3: These polymers can be prepared in water using the emulsion process. The monomers are mixed in a water / organ mixture. Solvent (preferably cyclohexane) is emulsified using an emulsifier, the reaction mixture is rendered inert by means of N ₂ and the reaction is then started after heating to 80 ° C. by adding suitable initiator or initiator systems (preferably Na ₂ S ₂ O ₈ ). The polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.

Process 4: These polymers can be prepared by the solution process in organic solvents (preferably toluene, for example also partially alcohols). The monomers are initially introduced in the solvent, the reaction mixture is rendered inert, and the reaction is then started after heating to 70 ° C. by adding suitable initiator or initiator systems (preferably dilauroyl peroxide). The polymers are isolated by evaporation of the solvent and subsequent vacuum drying. Polymers with hydrophobic side chains, uncrosslinked

Polymers with hydrophobic side chains, cross-linked

Polymers with hydrophobic side chains, cross-linked, grafted

Polymers with silicon-containing groups, uncrosslinked

Polymers with silicon-containing groups, cross-linked

Polymers with hydrophobic side chains and cationic groups, uncrosslinked u

Polymers with hydrophobic side chains and cationic groups, cross-linked

Polymers with fluorine-containing groups

Polymers with fluorine-containing groups, grafted

Multifunctional polymers

Chemical name of the reactants:

AMPS Acryloyldimethyltaurate, optionally Na or NH4 salt

Genapol ^® T-080 Ci ₆ -Ci8 fatty alcohol polyglycol ether with 8 EO units Genapol ^® T-110 Ci ₂ -Cι fatty alcohol polyglycol ether with 11 EO units Genapol ^® T-250 Ci ₆ -Cι ₈ fatty alcohol polyglycol ether with 25 EO units Genapol ^® LA-040 Cι ₂ -Ci ₄ fatty alcohol polyglycol ether with 4 EO units Genapol ^® LA-070 Ci ₂ -Cι fatty alcohol polyglycol ether with

7 EO units

Genapol ^® O-150 methacrylate Ci ₆ -C ₈ fatty alcohol polyglycol ether methacrylate with 15 EO units, Genapol ^® LA-250 crotonate Ci ₂ -C ₄ fatty alcohol polyglycol ether crotonate with

25 EO units Genapol ^® T-250 methacrylate Ci ₆ -Ci ₈ fatty alcohol polyglycol ether methacrylate with 25 EO units Genapol ^® T-250 acrylic Ci ₆ -Ci ₈ fatty alcohol polyglycol ether methacrylate with 25 EO units BB10 ^® polyoxyethylene (10) behenyl ether TMPTA trimethylolpropane triacrylate poly-NVP poly-N-vinylpyrrolidone Silvet ^® 867 siloxane polyalkylene oxide copolymer MBA methylene-bis-acrylamide AMA allyl methacrylate

© Y-12867 siloxane polyalkylene oxide copolymer Silvet ^® 7608 polyalkylene oxide modified

heptamethyltrisiloxane

Silvet ^® 7280 polyalkylene oxide modified

heptamethyltrisiloxane

DADMAC diallyldimethyl ammonium chloride

HEMA 2-hydroxyethyl methacrylate

Quat 2- (methacryloyloxy) ethyltrimethylammonium chloride

Fluowet ^® AC 600 perfluoroalkyl ethyl acrylate

Span ^® 80 sorbitan esters

The described, optionally feasible grafting of the copolymers with other polymers leads to products with a particular polymer morphology which result in optically clear gels in aqueous systems. A potential disadvantage of the copolymers without grafting is more or less strong opalescence in aqueous solution. This is based on previously unavoidable, over-crosslinked polymer fractions that arise during the synthesis and are only insufficiently swollen in water. As a result, light-scattering particles form, the size of which is well above the wavelength of visible light and are therefore the cause of opalescence. The described grafting process, which can be carried out as an option, significantly reduces or completely avoids the formation of over / replaced polymer components compared to conventional techniques.

The described, optionally feasible incorporation of both cationic charges and silicon, fluorine or phosphorus atoms into the copolymers leads to products which have special sensory and rheological properties in cosmetic formulations. An improvement in the sensory and theological properties may be desired in particular when used in rinse-off products (in particular hair treatment agents) as well as leave-on products (in particular O / W emulsions). Silicon-modified copolymers can take over the functions of silicone oils in part or in full. The copolymers can reduce or avoid the use of silicones.

The copolymers show advantageous properties both in crosslinked and in uncrosslinked form. While networked systems e.g. excellent property profiles with regard to emulsion stabilization could be thickened, especially with the help of the uncrosslinked variants, surfactant-containing solutions. The same applies to electrolyte-containing systems which are known to be very difficult or impossible to thicken with polyelectrolytes.

The copolymers have a wide range of uses and are suitable, for example, for use in formulations, emulsions, suspensions, dispersions and powders in aqueous-alcoholic, aqueous-surfactant formulations.

The copolymers can be used as thickeners for agents on an aqueous or aqueous-alcoholic basis, for example hair gels. The copolymers are furthermore suitable as stabilizers, dispersants and consistency agents for aqueous surfactant preparations, for example shampoos, shower baths, shower gels, foam baths and the like.

The thickening effect of the copolymers in aqueous surfactants is enhanced by an association of the polymer side chains and the surfactants and can be controlled by the choice of the side chains of the copolymers and by the choice of the surfactants. The suspending or dispersing and stabilizing action of the copolymers in aqueous surfactant is achieved by the association of the polymer side chains or functional groups in the main and side chain and the liquid components insoluble in aqueous surfactant, for example silicone oils or the insoluble components. for example zinc pyrethione.

The copolymers are also suitable as thickeners and dispersants, as emulsifiers, suspending agents with a thickening effect and as consistency agents for emulsions and suspensions, and as lubricants, adhesives, thickeners, Dispersant and emulsifier of decorative, solid-containing preparations. Mixtures of the copolymers can also be used. The emulsifying, stabilizing and / or consistency effect of the copolymers in emulsions is caused or enhanced by an association of the polymer side chains with one another, and by an interaction of the polymer side chains with the hydrophobic oil components.

The emulsions can be both water-in-oil emulsions and oil-in-water emulsions, microemulsions and multiple emulsions. The preparation of the emulsions can be carried out in a known manner, i.e. for example by hot, hot / cold or PIT emulsification. The non-aqueous proportion of the emulsions, which largely consists of the emulsifier, the thickener and the oil body, is usually 5 to 95% by weight, preferably 15 to 75% by weight. It follows that the emulsions can contain 5 to 95% by weight, preferably 25 to 85% by weight, of water, depending on whether lotions with a comparatively low viscosity or creams and ointments with a high viscosity are to be produced.

In a preferred embodiment, the copolymers are used in rinse-off products, preferably shampoos, shower baths, shower gels and foam baths.

In a further embodiment, the copolymers are used in leave-on products, preferably skin care products, day creams, night creams, skin care creams, nutritional creams, body lotions, ointments, sunscreens, lip care products and deodorants.

Furthermore, they are also suitable for surfactant-free, aqueous agents and emulsions, for example for hair treatments and hair rinses, hair gels but also for permanent wave agents, hair colorants, and for decorative cosmetics, for example make-ups, eye shadows, lipsticks, mascara and the like.

The compositions according to the invention contain, based on the finished compositions, preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, of copolymers. The agents according to the invention can contain anionic, cationic, non-ionic, hermaphrodite and / or amphoteric surfactants. The total amount of the surfactants used in the agents according to the invention (for example in the case of rinse-off products), based on the finished agents, is preferably 2 to 70% by weight, particularly preferably 5 and 40% by weight, particularly preferably 12 up to 35% by weight.

Preferred anionic surfactants are (C ₂ -C 20) -alkyl and alkylene-carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl amide sulfates and sulfonates, fatty acid alkyl amide polyglycol ether sulfates, alkane sulfonates, hydroxy alkanesulfonate, isolefinsulfonate, olefinsulfonate, olefinsulfonate, isolefinsulfonates, olefinsulfonate, olefinsulfonate, olefinsulfonate, isocyanates, and , Sulfosuccinates, sulfosuccinic acid semiesters and diesters, fatty alcohol ether phosphates, protein-fatty acid condensation products, alkyl monoglyceride sulfates and sulfonates, alkyl glyceride ether sulfonates, fatty acid methyl taurides, fatty acid sarcosinates, sulforicinoleates, acyl glutamates. These compounds and their mixtures are used in the form of their water-soluble or water-dispersible salts, for example the sodium, potassium, magnesium, ammonium, mono-, di- and triethanolammonium and analogous alkylammonium salts.

The proportion by weight of the anionic surfactants is preferably 2 to 30% by weight, particularly preferably 5 to 25% by weight, particularly preferably 12 to 22% by weight, based on the finished compositions.

Preferred cationic surfactants are quaternary ammonium salts, such as di (Cιo-C ₂₄ ) alkyl dimethylammonium chloride or bromide, preferably di (C ₂ -C _{8 8} ) alkyl dimethylammonium chloride or bromide; (Cι ₀ -C ₂₄ ) alkyl dimethyl ethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄ ) alkyl trimethyl ammonium chloride or bromide, preferably cetyl trimethyl ammonium chloride or bromide and (C2o-C ₂₂ ) alkyl trimethyl ammonium chloride or bromide; (C ₁₀ -C ₂₄ ) alkyl dimethylbenzyl ammonium chloride or bromide, preferably (Ci2-Cι ₈ ) alkyl dimethylbenzyl ammonium chloride; N- (-Cι-Cι ₈ ) alkyl pyridinium chloride or -bromide, preferably N- (-C ₂ -C ₁₆ ) alkyl-pyridinium chloride or bromide; N- (Cι ₀ - Cι ₈ ) alkyl isoquinolinium chloride, bromide or monoalkyl sulfate; N- (Ci ₂ -Cι ₈ ) alkyl polyoylaminoformylmethyl-pyridinium chloride; N- (Cι ₂ ~ Cι ₈ ) alkyl-N-methyl-morpholinium chloride, bromide or monoalkyl sulfate; N- (C ₁₂ -C ₈ ) alkyl-N-ethyl-morpholinium chloride, bromide or monoalkyl sulfate; (Ci6-Cι ₈ ) alkyl pentaoxethyl ammonium chloride; Diisobutyl-phenoxyethoxyethyldimethylbenzylammonium chloride; Salts of N, N-diethylaminoethylstearylamide and oleylamide with hydrochloric acid, acetic acid, lactic acid, citric acid, phosphoric acid; N-acylaminoethyl-NN-diethyl-N-methyl-ammonium chloride, bromide or monoalkyl sulfate and N-acylaminoethyl-N, N-diethyl-N-benzylammonium chloride, bromide or monoalkyl sulfate, with acyl preferably for Stearyl or oleyl.

The proportion by weight of the cationic surfactants is preferably 1 to 10% by weight, particularly preferably 2 to 7% by weight, particularly preferably 3 to 5% by weight.

Preferred nonionic surfactants are fatty alcohol ethoxylates

(Alkylpolyethylene glycols); Alkylphenolpolyethylenglykole;

Alkylmercaptanpolyethylenglykole; Fatty amine ethoxylates (alkylamino polyethylene glycols); Fatty acid ethoxylates (acyl polyethylene glycols);

Polypropylenglykolethoxylate (Pluronics ^®); Fatty,

(Fettsäureamidpolyethylenglykole); N-alkyl-, N-alkoxypolyhydroxy fatty acid amide,

Saccharoseester; Sorbitol ester and the polyglycol ether.

The weight fraction of the nonionic surfactants in the agents according to the invention (e.g. in the case of rinse-off products) is preferably in the range from 1 to

20% by weight, particularly preferably 2 to 10%, particularly preferably 3 to

7% by weight.

Preferred amphoteric surfactants are N- (-C ₂ -C ₁₈ ) -alkyl-ß-aminopropionate and N- (Ci ₂ - Cι ₈ ) -alkyl-ß-iminodipropionate as alkali and mono-, di- and trialkylammonium salts; N-acylaminoalkyl-N, N-dimethyl-acetobetaine, preferably N- (C ₈ -C ₈ ) -acyl-aminopropyl-N, N-dimethylacetobetaine; (C ₁₂ -C ₈ ) alkyl dimethyl sulfopropyl betaine; Amphoteric surfactants based on imidazoline (trade name: Miranol ^® , Steinapon ^® ), preferably the sodium salt of 1- (β-carboxymethyloxyethyl) -1- (carboxymethyl) -2-lauryl-imidazolinium; Amine oxide, for example (Ci2-Cι ₈ ) alkyl dimethylamine oxide, fatty acid amidoalkyl dimethylamine oxide.

The weight fraction of the amphoteric surfactants is preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight.

Preferred surfactants are lauryl sulfate, laureth sulfate, cocoamidopropyl betaine, sodium cocoyl glutamate, lauroamphoacetate.

In a preferred embodiment, the agents additionally contain co-surfactants from the group of alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines, amine oxides, fatty acid alkanolamides and polyhydroxyamides as foam-enhancing agents.

As further auxiliaries and additives, the agents according to the invention can contain oil bodies, emulsifiers and co-emulsifiers, as well as other additives commonly used in cosmetics, such as e.g. cationic polymers, film formers, superfatting agents, stabilizers, biogenic agents, glycerin, preservatives, pearlescent agents, colorants and fragrances, solvents, opacifiers, also protein derivatives such as gelatin, collagen hydrolyzates, polypeptides on a natural and synthetic basis, egg yolk, lecithin, lanolin and lanolin derivatives, fatty alcohol , Silicones, deodorising agents, substances with keratolytic and keratoplastic effects, enzymes and carrier substances. Furthermore, antimicrobial agents can be added to the agents according to the invention

Oil body means any fatty substance that is liquid at room temperature (25 ° C). The fat phase can comprise one or more oils, which are preferably selected from the following oils: Silicone oils, volatile or non-volatile, linear, branched or ring-shaped, possibly organically modified; Phenyl silicones, silicone resins and rubbers that are solid or liquid at room temperature; Mineral oils such as paraffin or petroleum jelly; Oils of animal origin, such as perhydrosqualene or lanolin; Oils of vegetable origin, such as liquid triglycerides, for example sunflower, corn, soybean, rice, jojoba, babusscu, pumpkin, grape seed, sesame, walnut, apricot, macadamia, avocado, sweet almond , Meadow foam, castor oil, triglycerides of caprylic / capric acids, olive oil, peanut oil, rapeseed oil and coconut oil; synthetic oils, such as purcellin oil, isoparaffins, linear and / or branched fatty alcohols and fatty acid esters, preferably Guerbet alcohols having 6 to 18, preferably 8 to 10, carbon atoms; Esters of linear (C ₆ -C ₃ ) fatty acids with linear (C6-C ₂ o) fatty alcohols; Esters of branched (C ₆ -C ι ₃ ) carboxylic acids with linear (C6-C ₂ o) fatty alcohols; Esters of linear (Ce-Ci ₈ ) fatty acids with branched alcohols, especially 2-ethylhexanol; Esters of linear and / or branched fatty acids with polyhydric alcohols (such as dimer diol or trimer diol) and / or Guerbet alcohols; Triglycerides based on (C ₆ -Cιo) fatty acids; Esters such as dioctyl adipate, diisopropyl dimer dilineloat; Propylene glycols / dicaprilat or waxes such as beeswax, paraffin wax or microwaxes, optionally in combination with hydrophilic waxes, such as, for example, cetylstearyl alcohol; fluorinated and perfluorinated oils; fluorinated silicone oils; Mixtures of the aforementioned substances.

The non-ionic co-emulsifiers include Storage products of 0 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear

Fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms, on alkylphenols with 8 to 15 carbon atoms in the alkyl group and on sorbitan or sorbitol esters; (Cι ₂ -Cι ₈ ) fatty acid monoesters and diesters of adducts of 0 to 30 moles of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters, such as Polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate. Mixtures of compounds from several of these classes of substances are also suitable.

Suitable ionogenic co-emulsifiers are e.g. anionic emulsifiers, such as mono-, di- or tri-phosphoric acid esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.

Suitable cationic polymers are those known under the INCI name "Polyquaternium", in particular Polyquaternium-31, Polyquaternium-16, Polyquaternium-24, Polyquaternium-7, Polyquaternium-22, Polyquaternium-39, Polyquaternium-28, Polyquaternium-2, Polyquaternium -10, Polyquaternium-11, as well as Polyquaternium 37 & mineral oil & PPG trideceth (Salcare SC95), PVP-dimethylaminoethyl methacrylate copolymer, guar hydroxypropyltriammonium chlorides, as well as calcium alginate and ammonium alginate. Cationic cellulose derivatives; cationic starch and copolymers can be used; ; quaternized vinylpyrrolidone / vinylimidazole polymers; condensation products of polyglycols and amines; quaternized collagen polypeptides; quaternized wheat polypeptides; polyethyleneimines; cationic silicone polymers such as amidomethicones;

Copolymers of adipic acid and dimethylaminohydroxy-propyldiethylenetriamine; Polyaminopolyamide and cationic chitin derivatives such as chitosan. Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine and / or alkyl-modified silicone compounds, and also polyalkylsiloxanes, polyalkylarylsiloxanes, polyether siloxane copolymers, as in US 5104 645 and the writings described therein, which can be both liquid and resinous at room temperature.

Depending on the application, suitable film formers are water-soluble polyurethanes, for example C10-polycarbamylpolyglyceryl esters, polyvinyl alcohol, polyvinylpyrrolidone, copolymers, for example vinylpyrrolidone / vinyl acetate copolymer, water-soluble acrylic acid polymers / Copolymers or their esters or salts, for example partial ester copolymers of acrylic / methacrylic acid and polyethylene glycol ethers of fatty alcohols, such as acrylate / steareth-20-methacrylate copolymer, water-soluble cellulose, for example hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-soluble quaterniums, polyquaterniums, carboxyvinyl polymers, such as carbovinyl polymers ere and their salts, polysaccharides, for example polydextrose and glucan.

Substances such as, for example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers. For example, isopropyl palmitate, glycerin and / or sorbitol are available as a moisturizing substance.

Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate can be used. Biogenic active substances are understood to mean, for example, plant extracts and vitamin complexes.

In addition, the formulations according to the invention can be organic

Contain solvents. In principle, all monohydric or polyhydric alcohols are suitable as organic solvents. Alcohols with 1 to 4 carbon atoms such as ethanol, propanol, isopropanol, n-butanol, i-butanol, t-butanol, glycerol and mixtures of the alcohols mentioned are preferably used. Other preferred alcohols are polyethylene glycols with a relative

Molecular weight below 2000. In particular, use of polyethylene glycol with a relative molecular weight between 200 and 600 and in amounts of up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 to 25% by weight is preferred , Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol. The agents according to the invention can be mixed with conventional ceramides, pseudoceramides, fatty acid-N-alkylpolyhydroxyalkylamides, cholesterol, cholesterol fatty acid esters, fatty acids, triglycerides, cerebrosides, phospholipids and similar substances as a care additive.

Suitable UV filters are e.g. 4-aminobenzoic acid; 3- (4'-trimethylammonium) benzylidene-borane-2-one methyl sulfate; 3,3,5-trimethyl-cyclohexyl salicylate; 2-hydroxy-4-methoxybenzophenone; 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts; 3,3 '- (1,4-phenylenedimethine) bis (7,7-dimethyl-2-oxobicyclo [2.2.1] heptane-1-methanesulfonic acid and its salts; 1- (4-tert-butylphenyl) -3- (4-methoxyphenyϊ) propan-1, 3-dione, 3- (4'-sulfo) -benzyϊιden-bornan- 2-one and its salts; 2-cyan-3,3-diphenyl-acrylic acid- (2nd -ethylhexyl ester); polymer of N- [2 (and 4) - (2-oxoborn-3-ylidenemethyl) benzyl] acrylamide; 2-ethylhexyl 4-methoxycinnamate; ethoxylated ethyl 4-aminobenzoate; Re-isoamyl 4-methoxycinnamate; 2,4,6-tris- [p- (2-ethylhexyloxycarbonyl) an ilino] -1,3,5-triazine;

2- (2H-benzotriazol-2-yl) -4-methyl-6- (2-methyl-3- (1, 3,3,3-tetramethyl-1- (trimethylsilyloxy) disiloxanyl) propyl) phenol; 4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylamino] -1, 3,5-triazin-2,4-yl) diimino] bis- (benzoic acid-2 - ethylhexyl ester); S - ^ - MethylbenzylidenJ-D, L-camphor; 3-benzylidene-camphor; Salicylic acid 2-ethylhexyl ester; 4-dimethylaminobenzoic acid 2-ethylhexyl ester; Hydroxy-4-methoxy-benzophenone-5-sulfonic acid (Sulisobenzonum) and the sodium salt; and / or 4-isopropylbenzyl salicylate.

As pigments / micropigments, e.g. microfine titanium dioxide, mica titanium oxide, iron oxides, mica iron oxide, zinc oxide, silicon oxides, ultramarine blue, chromium oxides can be used.

Suitable antioxidants are, for example, superoxide dismutase, tocopherol (vitamin E) and ascorbic acid (vitamin C). Examples of suitable preservatives are phenoxyethanol, parabens, pentanediol or sorbic acid.

The dyes which can be used are those which are suitable and approved for cosmetic purposes.

Suitable antifungal active ingredients are preferably ketoconazole, oxiconazole, terbinafine, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole fluonazole, ionifoneazonazole, ioconazole, ioconazole, ioconazole, ioconazole, ioconazole, ioconazole, ionoconazole, ioconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionoconazole, ionocone, ionoconazole

In order to adjust the rheological properties of aqueous or solvent-containing emulsions or suspensions, a large number of different systems are specified in the specialist literature. For example, cellulose ethers and other cellulose derivatives (e.g. carboxymethyl cellulose, hydroxyethyl cellulose), gelatin, starch and starch derivatives, sodium alginates, fatty acid polyethylene glycol esters, agar agar, tragacanth or dextrins are known. Various materials are used as synthetic polymers, e.g. Polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers from the above. Compounds, including their various salts and esters. These polymers can optionally be cross-linked or uncross-linked.

It is essential for the invention that the described copolymers containing acryloyldimethyltauric acid can also be used without the use of an additional co-emulsifier and / or without the use of an additional consistency agent. The use of co-emulsifiers and / or consistency enhancers is therefore not mandatory, but possible. A combination with other known co-emulsifiers and / or Consistency agents may be desirable for setting special cosmetic profiles and for exploiting synergistic effects.

The agents according to the invention are usually adjusted to a pH in the range 2 to 12, preferably pH 3 to 8.

The nature of the agents according to the invention is extremely advantageous: the emulsions are creamy and ointment-like and do not have the gel-like or even gelatin-like appearance of certain prior art emulsions in which the outer aqueous phase is thickened.

The cosmetic feeling on the skin is also very good: when applied, the emulsion gives a feeling of freshness and comfort, while at the same time having a rich and nourishing effect; it is soft and comfortable and in no way sticky.

The following examples and applications are intended to explain the invention in more detail without, however, restricting it thereto (all percentages are% by weight). The copolymers used in the examples are representatives of the particularly preferred copolymers No. 1 to No. 67 already listed in the description. The preparation was carried out according to processes 1, 2, 3 or 4 using the preferred initiators and solvents.

Example 1: O / W - skin milk

composition

A copolymer No. 21 0.50%

Isopropyl palmitate 4.00% almond oil 5.00% 4.00%

Wheat germ oil 1.00%

^® Cetiol SN (Henkel) 8.00% Cetearyl isononanoate B ^® Aristoflex AVC (Clariant) 0.30%

Ammonium Acryloyldimethyltaurate / VP Copolymer C water ad 100% D fragrances 0.30%

manufacturing

Mix I A and B, then add C.

II Stir D to 1 III Homogenize the emulsion

Example 2: O / W after-sun milk

Composition: A copolymer No. 34 1.00%

Isopropyl palmitate 5.00%

^® Cetiol SN (Henkel) 4.00% cetearyl isononanoate

Soybean oil 4.00% ^® Miglyol 812 (Dynamit Nobel) 3.00%

Capryl / Caprin triglycerides

Jojoba oil 3.00%

Wheat germ oil 1.00%

D ^® AQUAMOLLIN BC PIv. hochkonz. (Clariant) 0.10% ethylenediamine tetraacetic acid sodium salt

Citric acid (10%) 0.30%

Water 68.80%

Glycerin 3.00%

ALLANTOIN (Clariant) 0.20% allantoin

Preservatives q.s.

E ethanol 1, 50%

Perfume oil 0.30% manufacturing

I Mix the components of A homogeneously

II Stir D into I at approx. 35 ° C.

III Homogenize the emulsion.

Example 3: W / O cream

composition

A ^® HOSTACERIN DGI (Clariant) 4.00%

Polyglyceryl-2 sesquiisostearate

Beeswax 2.00%

Copolymer No. 10 1.5%

Mineral Oil, low viscosity 5.00%

Vaseline 10.00%

^® Cetiol V (Henkel KGaA) 5.00%

Decyl oleate

B 1, 2-propylene glycol 3.00%

Water 69.10%

Preservative q.s.

C Fragrance 0.40%

manufacturing

I Melt at 80 ° C

II B heat to 80 ° C.

III Stir II into I.

IV Stir until cool.

V At 35 ° C add C to IV. Examples of surfactant formulations

Example 4: body wash

composition

A ^® GENAPOL LRO liquid (Clariant) 40.00% sodium laureth sulfate

B Fragrance 0.30%

C water 52.70%

Dyestuff q.s.

Preservative q.s.

^® GENAGEN LDA (Clariant) 6.00%

Disodium lauroamphodiacetate

Citric Acid q.s. D copolymer No. 44 1.00%

manufacturing

Stir I B into A.

II Add components from C one after the other to I. III Adjust pH to 5.5

IV Adjust the viscosity by stirring D into II

Example 5: Baby Shampoo

composition

A water ^* 60.70%

^® GENAPOL ZRO liquid (Clariant) 25.00%

Sodium Laureth Sulfate

^® HOSTAPON CLG (Clariant) 8.00%

Sodium lauroyl glutamate

^® GENAPOL SBE (Clariant) 5.00%

Disodium Laureth Sulfosuccinate

Fragrance 0.30% Dyestuff solution qs

Preservative q.s.

B Copolymer No. 44 1.00%

manufacturing

Solve I B in A.

II adjust pH if necessary

Example 6: Anti-dandruff shampoo, clear

composition

A ®OCTOPIROX (Clariant) 0.50%

Piroctone olamine

B water 10.00% C ^® GENAPOL LRO LIQUID (Clariant) 30.00%

Sodium Laureth Sulfate

D ^® Belsil DMC 6032 (Wacker Chemie 1.50%

Dimethicone Copolyol Acetate

Fragrance 0.30% E ^® ALLANTOIN (Clariant) 0.30%

F water 46.40%

G Dyestuff solution q.s.

Panthenol (Hoffmann La Röche) 1.00%

^® GENAGEN GAB (Clariant) 8.00% cocamidopropyl betaine

H copolymer No. 28 1, 10%

manufacturing

Mix I A with B, stir II C into I until the solution is clear

III Add components from D to I one after the other

IV Stir in F while warming and then stir in I.

V Add components from G to I one after the other VI adjust pH if necessary

VII Adjust the viscosity by stirring H in

Example 7: Anti-dandruff shampoo, pearlescent

composition

A water 38.7%

B ^® HOSTAPON SCI-65 (Clariant) 3.00% sodium cocoyl isethionate

C ^® GENAPOL LRO liquid (Clariant) 35.00%

Sodium Laureth Sulfate

^® HOSTAPON KCG (Clariant) 5.00%

Sodium Cocoyl Glucamate ^® Belsil DMC 6032 (Wacker) 1.00%

Dimethicone Copolyol Acetate

Fragrance 0.30%

^® GENAGEN GAB (Clariant) 9.00%

^® Cocamidopropyl Betaine GENAPOL TSM (Clariant) 4.00%

PEG-3 Distearate (and) Sodium Laureth Sulfate

Merquat 550 0.50%

Polyquaternium-7

Zinc Omadine FPS (Olin) Zinc Pyrithione (48%) 2.50%

Copolymer No. 14 1.00%

Dyestuff solution q.s.

Preservative q.s.

manufacturing

I Loosen B in A at 80 ° C

II After cooling to approx. 35 ° C, add components C one after the other Examples of gels

Example 8: Hair gel with conditioning properties

A water 92.00%

Panthenol 1, 50%

UVAsorb S5 0.05%

Benzophenone-4

Dyestuff solution q.s.

Preservative q.s.

B ^® Emulsogen HCO 040 (Clariant) 0.50% PEG-40 Hydrogenated Castor Oil parfume qs

C copolymer No. 26 2.00%

D Gafquat 755N (ISP) 2.50% polyquaternium-11

Production I Mix components A.

II Mix components B and add to I.

III Give C to D to I.

Example 9: Hair gel with strong hold

composition

A water 91, 50%

PVP K-30 (ISP) 4.00

PVP

Panthenol 0.50% UVAsorb S5 0.05%

Benzophenone-4

Dyestuff solution q.s.

Preservative qs B Abil B 8851 (Goldschmidt) 1.00%

Dimethicone copolyol

^® Emulsogen HCO 040 (Clariant) 0.50%

PEG-40 Hydrogenated Castor Oil parfume q.s.

Copolymer No. 63 2.50%

manufacturing

I mix components A II add components B to I III add components C to I.

Claims

claims: 1. Cosmetic, dermatological and pharmaceutical agents, characterized in that they contain at least one copolymer, obtainable by radical copolymerization of A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates, B) optionally one or more further olefinically unsaturated, non-cationic, optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, C) optionally one or more olefinically unsaturated, cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, D) optionally one or more at least monofunctional radicals capable of radical polymerization, silicon-containing component (s), E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization, F) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each having at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number-average molecular weight greater than or equal to 200 g / mol, where it is in the Macromonomers are not silicon-containing component D) or fluorine-containing component E), G) the copolymerization optionally taking place in the presence of at least one polymeric additive with number-average molecular weights of 200 g / mol to 10 ⁹ g / mol, H) with the proviso that component A) is copolymerized with at least one component selected from one of groups D) to G). 2. Composition according to claim 1, characterized in that the comonomers B) are unsaturated carboxylic acids, salts of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, esters of unsaturated carboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with 1 to 22 C- Atoms, open-chain N-vinylamides, cyclic N-vinylamides with a ring size of 3 to 9, amides of acrylic acid, amides of methacrylic acid, amides of substituted acrylic acids, amides of substituted methacrylic acids, 2-vinylpyridine, 4-vinylpyridine, vinyl acetate; Styrene, acrylonitrile, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or its esters or salts, vinylsulfonic acid or its esters or salts, allylphosphonic acid or its esters or salts and / or methallylsulfonic acid or its esters or salts. 3. Composition according to claim 1 and / or 2, characterized in that it is the comonomers C) Diallyldimethylammonium chloride (DADMAC), [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC), [2- (acryloyloxy) ethyl] trimethylammonium chloride, [2-methacrylamidoethyl] trimethylammonium chloride, [2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinyl pyridinium chloride N-methyl-4-vinyl pyridinium chloride dimethylaminoethyl Dimethylaminopropyl methacrylamide, methacryloylethyl-N-oxide and / or Methacryloylethyl betaine. 4. Composition according to at least one of claims 1 to 3, characterized in that the silicon-containing components D) are compounds of the formula (I) R ¹ - Z- [(Si (R ³ R ⁴ ) -O-) _w - (Si (R ⁵ R ⁶ ) -O) _x -] - R ² (I), where R ^{1 is} a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, Represents senecionyl, itaconyl, maleinyl, fumaryl or a styryl radical; Z is a chemical bridge, preferably selected from -O-, - ((Ci - Cβo) Alkylene) -, - ((C ₆ - C ₃₀ ) arylene) -, - ((C ₅ - C ₈ ) cycloalkylene) -, - ((C Cβo) alkenylene) -, - (polypropylene oxide) _n -, - (polyethylene oxide ) ₀ -, - (polypropylene oxide) n (polyethylene oxide) ₀ -, where n and o independently of one another represent numbers from 0 to 200 and the distribution of the EO / PO Units can be statistical or block-shaped; - ((Ci - C ₁₀ ) alkyl) - (Si (OCH ₃ ) ₂ ) - and - (Si (OCH ₃ ) ₂ ) -; R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another -CH ₃ , -O-CH ₃ , -C ₆ H ₅ or -OC _δ mean Hδ; w, x are numbers from 0 to 500, where either w or x must be greater than zero, and R ^{2 is} a saturated or unsaturated, aliphatic cycloaliphatic, arylaliphatic or aromatic radical each having 1 to 50 C atoms or a group of the formulas -OH , -NH ₂ , -N (CH ₃ ) ₂ , -R ⁷ or a group -ZR ¹ means, where Z and R ^{1 have} the meanings given above and R ^{7 is} a group of the formula -O-Si (CH ₃ ) ₃ , -O-Si (phenyl) ₃ , -O-Si (O-Si (CH ₃ ) ₃ ) ₂ CH ₃ ) and -O-Si (O -Si (Ph) ₃ ) ₂ Ph) means. 5. Composition according to at least one of claims 1 to 4, characterized in that the fluorine-containing components E) are compounds of the formula (II) R ¹ -YC _r H ₂ rC _s F _2s CF ₃ (II), where R ^{1 is} a polymerizable function from the group of vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic -, crotonyl, senecionyl, itaconyl, maleinyl, Represents fumaryl or styryl; Y is a chemical bridge, preferably -O-, -C (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ -CH (OH) -CH ₂ -O-, -O-SO ₂ -O-, -OS (O) -O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH-, -N (CH ₃ ) -, -O- (-C-C ₅₀ ) alkyl-O -, -O-phenyl-O-, -O-benzyl-O-, -O- (C ₅ -C ₈ ) cycloalkyl-O-, -O- (C ₁ -C ₅₀ ) alkenyl-O-, -O - (CH (CH ₃ ) -CH ₂ -O) _n -, -O- (CH ₂ -CH ₂ -O) _n - and -O - ([CH-CH ₂ -O] n- [CH2-CH2- O] m) o-, where n, m and o independently represent numbers from 0 to 200, and r, s represent stoichiometric coefficients which are independently numbers between 0 and 200. 6. Composition according to at least one of claims 1 to 5, characterized in that the macromonomers F) are compounds of the formula (III), R ¹ - Y - [(A) v - (B) _w - (C) _x - (D) _z ] - R ² (IM) where R ^{1 is} a polymerizable function from the group of the vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, methylvinyl , Acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or Represents styryl; Y is a bridging group, preferably -O-, -S-, -C (O) -, -C (O) -O-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ -CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO ₂ -O-, -O-SO- O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -; A, B, C and D are independently discrete chemical Repeat units, preferably originating from acrylamide, Methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, Isoprene, isobutene, diethylacryiamide and diisopropylacrylamide, particularly preferably ethylene oxide, propylene oxide; v, w, x and z are independently 0 to 500, preferably 1 to 30, the sum of v, w, x and z being ≥ 1 on average; and R ^{2 represents} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C ₅₀ ) hydrocarbon radical, OH, -NH ₂ or -N (CH ₃ ) or is equal to [-YR ¹ ]. 7. Composition according to at least one of claims 1 to 6, characterized in that the polymeric additives G) are homo- or copolymers of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N- Vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxymethyl methacrylate, diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols. 8. Composition according to at least one of claims 1 to 7, characterized in that the copolymerization is carried out in the presence of at least one polymeric additive G). 9. Composition according to at least one of claims 1 to 8, characterized in that the copolymers are crosslinked. 10. Composition according to at least one of claims 1 to 9, characterized in that the copolymers are prepared by precipitation polymerization in tert-butanol. 11. Agent according to at least one of claims 1 to 10, characterized in that it contains, based on the finished agent, 0.01 to 10 wt .-% of the copolymers. 12. Composition according to at least one of claims 1 to 11, characterized in that the copolymers are water-soluble or water-swellable.