DE19919774A1 - New combinations of sulfonated comb polymers and physiologically compatible anionic or amphoteric polymers, used especially in cosmetic hair preparations, e.g. fixing sprays - Google Patents

Abstract

Combinations of (a) water-soluble and/or -dispersible comb polymers with sulfone group-containing polyester side chains attached to the main chain by ester groups and (b) one or more substances selected from physiologically compatible anionic or amphoteric polymers. An Independent claim is also included for cosmetic hair preparations containing effective amounts of such combinations.

Description

The present invention relates to novel sulfonated comb polymers and preparations, containing such sulfonated comb polymers. In particular, the present Er finding hair-cosmetic active ingredients and preparations for strengthening, shaping, Strengthening and structural improvement of the hair.

An appealing-looking hairstyle is now generally considered an indispensable part of one looked after cultivated exteriors. It is due to current fashion trends Again and again, hairstyles are chic, which are only used on many hair types certain solidifying active ingredients build up or maintain for a longer period receive.

For these reasons, some hair care cosmetics are used for some time, which are intended to be rinsed out after exposure to the hair, partly those which should remain on the hair. The latter can be formulated in this way that they not only serve the care of the individual hair, but also the exterior improve hairstyle overall, for example, by giving the hair Give more fullness, fix the hairstyle over a longer period of time or his Improve manageability.

The property of fullness is attributed to a hairstyle, for example, when the hair after the treatment does not lie flat on the scalp and is easy to style.

The property of volume is attributed to a hairstyle, for example, if that Hair after treatment has fullness and bounce.  

The property of the body is attributed to a hairstyle, for example, if that Hair volume remains large even under external, disturbing influences.

Firming agents, which are usually polymeric compounds can be incorporated into common hair cleansing or conditioning agents. In In many cases, however, it is advantageous to use them in the form of special remedies such as hair fixatives or To apply hair sprays.

There have recently been a number of developments in the hair cosmetics field, the a need for novel fixing active ingredients or new Formulierungsfor awakened men. Many of these developments are not based on application technical disadvantages or shortcomings of the known means, but z. B. on Environmental considerations, legal requirements or other "non-technical" Causes.

In particular, there is a growing shift from funds based on volatile organic compounds Compounds (so-called "volatile organic compounds" or in short: VOC's), eg. B. Alcohols, aimed at water-based agents.

However, the state of the art leaves it open to active ingredients (polymers) and preparations lack, which correspond to the aforementioned requirements. The haircut fi xierende preparations of the prior art, for example, usually contain Ingredients (synthetic or natural polymers), which are at risk, in part or complete replacement of volatile organic compounds with water Significant impairment of product properties, often through clever formulation must be compensated. In addition, the fixative Preparations of the prior art often by difficult or expensive too formulating formulation ingredients with insufficient long-term stability, wherein this applies especially to silicone derivatives which improve flexibility and Tactility of the polymer film surface can be used.

It was therefore the task to develop appropriate means with regard to technical properties, such as the spray behavior and the Drying time of hair sprays meeting consumer expectations  and at the same time a reduced amount of volatile organic compounds without the elemental properties of the polymer film on the hair, such as z. Clarity, transparency, surface tactility, gloss, elasticity and washability be negatively influenced and the processability of the formulation ingredients easy and unproblematic.

It has now been found, and therein is the solution to the problems that com binations from

• a) water-soluble and / or water-dispersible comb polymers consisting from a polymer main chain and with this polymer main chain via ester group pen linked sulfongruppenhaltigen polyester side arms

and

• a) one or more substances selected from the group of physiologically ver suitable anionic or amphoteric polymers

or hair cosmetic preparations containing an effective amount of Kombinatio NEN

• a) water-soluble and / or water-dispersible comb polymers consisting from a polymer main chain and with this polymer main chain via ester group pen linked sulfongruppenhaltigen polyester side arms

and

• a) one or more substances selected from the group of physiologically ver suitable anionic or amphoteric polymers

eliminate or at least mitigate the disadvantages of the prior art.

The combinations of the invention are characterized by both good water and Alcohol compatibility as well as favorable film properties and high Netzver like out. Moreover, they are easy to formulate.

The basic structure of the comb polymers used according to the invention follows essentially the following scheme:

The interconnected groupings named XXX mean the main body of a polymer backbone, on which via ester molecules groupings, which bear the name YYY. The molecule group YYY represents both the complete sulfonic polyester side However, the comb polymers used according to the invention may be others Represent molecular groupings.

The polymeric main chain of the comb polymers used according to the invention preferably consists of:

• a) polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or derivatives thereof such as polyacrylic acid, polymethacrylic acid and their esters (esters of the two acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid, maleic anhydride, fumaric acid and polynorboric acid. The average molecular weights of the polycarboxylic acid used can be between 200 and 2,000,000 g / mol, the range of 2,000-100,000 g / mol preferably being used.

The average molecular weights of the polycarboxylic acid used can be between 200 and 2,000,000 g / mol wherein the range of 2,000-100,000 g / mol is preferably Ver finds application.

The attachment of the polyester side chains via an ester group, by the Reaction of a functional group of the main chain (-COOH in the case of polycarbon acids or -OH in the case of the polyalcohols) with a corresponding group of the poly esters (OH in the case of the polycarboxylic acids and COOH in the case of the polyalcohols). itself Reactive derivatives of the above-mentioned components can also be understood For example, anhydrides, esters, halogen compounds and such more).

The comb polymers used according to the invention may advantageously be distinguished by the following structural formulas:

etc.

Here, p and o can be chosen so that the previously designated mean moles Kulargewichte the used main chain components come about.

The polyester side chains according to formula I-III advantageously consist of:
G: an aromatic, aliphatic or cycloaliphatic organyl units containing at least two terminal oxygen atoms and having a carbon number of C ₂ to C ₂₂ or derivatives of a polyglycol of the formula HO- [R ³ -O) _k - [R ⁴ -O) _m -H, correspondingly an organyl unit

The radicals R ³ and R ⁴ represent alkylene radicals having a carbon number of C ₂ -C ₂₂ , where both radicals need not necessarily be different.

For the coefficients k and m the following applies: k + m ≧ 1, where k and m can furthermore be chosen so that the previously described mean molecular weights of the inserted main chain components are obtained.
D: an at least two terminal acyl-containing aromatic, ali phatic or cycloaliphatic organyl moiety having a carbon number of C ₂ to C ₂₂ , wherein also combinations of several different acid components can be contained in the claimed target molecule, for example an organyl moiety of the scheme

where R ^{s can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals having carbon numbers of C ₂ to C ₂₂ .
T: a compound from the group of at least two terminal acyl-containing sulfonated aromatic, aliphatic or cycloaliphatic Or ganylverbindungen
R ¹ : may mean lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl positions of the amines independently of each other with C ₁ to C ₂₂ alkyl radicals and 0 to 3 hydroxyl groups are occupied.
R ² : a molecule residue selected from the groups of

• aromatic, aliphatic or cycloaliphatic amino functions: (-NH-R ⁵ , -NR ⁵ ₂ where R ^{5 may be} an alkyl or aryl radical with C ₁ to C ₂₂ )
• aromatic, aliphatic or cycloaliphatic monocarboxylic acid groups: (-COOR ⁶ where R ^{6 represents} an alkyl or aryl radical with C ₁ to C ₂₀₀ )
• - via ether functions bridged aromatic, aliphatic or cycloaliphatic rule organyl radicals: (-OR ⁵ )
• - Via ether functions bridging polyalkoxy compounds of the form
  -O- [R ⁷ -O] _q - [R ⁸ -O] _r -Y
  The radicals R ⁷ and R ⁸ are advantageously alkylene radicals having a carbon number of C ₂ -C ₂₂ , where both radicals do not necessarily have to be different. The radical Y can be both hydrogen and aliphatic with C ₁ -C ₂₂ . For the coefficients q and r: q + r ≧ 1.
• - Via ether functions bridging singly or multiply ethoxylated sulfo-ned organyl or preferably their alkali metal or alkaline earth metal salts, as for example advantageously characterized by the generic structural formula
  - (O-CH ₂ -CH ₂ ) _s -SO ₃ R ¹
  with s ≧ 1, and wherein s can also be chosen so that the previously designated mean molecular weights of the main chain constituents used come about.
  Of course, the functionality of the components used according to the invention is not limited to the use of OH groups, but also includes COOH end groupings or mixtures of both, wherein it also applies here that at least two COOH groups must be present in the molecule freely. Reactive derivatives such as anhydrides, esters, epoxides or halides are of course also usable.

The average molecular weights of the comb polymers used according to the invention are NEN advantageously between 200 and 2,000,000 g / mol are, particularly advantageous between 200 and 100,000 g / mol, with the range of 1,000-30,000 g / mol being preferred Use is found, very particularly advantageous from 5,000 to 15,000 g / mol.

The comb polymers used according to the invention are advantageously prepared by Esterification or transesterification of the underlying functional alcohol components  and diols with the carboxylic acids or their suitable derivatives (for example Alkyl esters, halides and the like) in the presence of an esterification catalyst such as alkali metal hydroxides, their carbonates and acetates, alkaline earth metal oxides, -hy hydroxides, carbonates and acetates, as well as alkali metal and alkaline earth metal salts of fat acids having 6 to 22 carbon atoms. Furthermore come titanium compounds, such as Tita nate, metallic tin and organic tin compounds such as mono- and dialkyltin derivatives as esterification catalysts into consideration. Preferably, the esterification / Um esterification using tin ground or titanium tetraisopropylate as a catalyst carried out.

The esterification / transesterification is preferred at temperatures of 120 ° C to 280 ° C. carried out, wherein the resulting lower-boiling condensate (alcohols or What Ser) is removed by distillation from the condensation product, preferably under vermin dertem pressure up to <0.1 mbar.

As starting materials for the polyester skeleton comb polymers according to the invention can polyme re aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their De derivatives such as polyacrylic acid, polymethacrylic acid and their esters (esters of the two acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid , Maleic anhydride, fumaric acid and polynorbornene acid. The average molecular weights of the individual polycarboxylic acids can be between 200 and 2,000,000 g / mol, the range of 2,000-100,000 g / mol preferably being used.

Also random or block copolymers of the above class of compounds with other vinylic monomers such as styrene, acrylamide, α-methylstyrene, Styrene, N-vinylpyrrolidone, N-vinylcaprolactone, acrylamidopropylensulfonic acid and their Alkali, alkaline earth and ammonium salts, MAPTAC (methacrylamidopropyltrimethyl ammonium chloride), DADMAC, vinylsulfonic acid, vinylphosphonic acid, crotonic acid, Vinylacetamide, vinylmethylacetamide, vinylforamide, acrylic acid or methacrylic acid vate (for example, free acid or ester), or acrylamide derivatives or vinyl acetate may serve to form the polymeric backbone.  

As a basis for at least two terminal oxygen atoms containing aromatic, aliphatic or cycloaliphatic Organyleinheiten having a carbon number of C ₂ to C ₂₂ or derivatives of a polyglycol of the form HO- [R ³ -O) _k - [R ⁴ -O) _m -H bi functional alcohol components are used.

At least difunctional aromatic, aliphatic or cycloaliphatic alcohols having a carbon number of C ₂ to C ₂₂ or a polyglycol of the form HO- [R ³ -O] _k - [R ⁴ -O] _m -H are particularly suitable for this purpose. The radicals R ³ and R ⁴ represent alkyl radicals having a carbon number of C ₂ to C ₂₂ , where both radicals may be identical or different. For the coefficients k and m the following applies: k + m ≧ 1, where k and m can furthermore be chosen such that the previously described average molecular weights of the main chain constituents used are obtained.

It may be of particular advantage, instead of using difunctional alcohol components, to use tri-, tetra- or generally polyfunctional alcohol components, for example selected from the following group, before some of them:

As a basis for at least two terminal acyl-containing aromatic, ali phatic or cycloaliphatic Organyleinheiten having a carbon number of C ₂ to C ₂₂ , for example, organyl moieties of the scheme

For example, it is possible to use aromatic and linear or cyclic, saturated or unsaturated aliphatic carboxylic acids having a carbon number of C ₂ to C ₂₂ or its anhydrides, for example phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, brassylic acid. Combinations of several different acid components are possible as mono mereinheit in the claimed target molecule.

Suitable sulfone-containing monomers are sulfonated aromatic, aliphatic or cycloaliphatic dialcohols, diacids or their esters, such as sulfosuccinic acid, 5-sulfoisophthalic acid or its alkali metal or alkaline earth metal salts or mono-, di-, tri- or tetraalkylammonium salts with C ₁ to C ₂₂ - alkyl radicals. Among the alkali salts, lithium and sodium salts are particularly preferred.

Also suitable are aromatic, aliphatic or cycloaliphatic amines having C ₁ to C ₂₂ alkyl or aryl radicals and / or aromatic, aliphatic or cycloaliphatic monocarboxylic acids having C ₁ to C ₂₀₀ alkyl or aryl radicals and / or polyalkoxy compounds of the formula -O- [R ⁷ -O] _q - [R ⁸ -O] _r -X, where the radicals R ⁷ and R ^{8 are} alkyl radicals which may be the same or different carbon number of C ₂ to C ₂₂ and the radical X is both hydrogen and aliphatic Nature with C ₁ -C ₂₂ can be and the coeffi cients q and r: q + r ≧ 1 are used.

Also suitable are sulfonated mono- or polyethylene glycols or, preferably, their alkali metal or alkaline earth metal salts: (H- (O-CH ₂ -CH ₂ ) _s -SO ₃ R ¹ with s ≧ 1, where s can furthermore be chosen such that the above designated average molecular weights of the main chain components used.)

For the preparation of comb polymers used in the invention, the Forming the side chain used alcohols and acids or esters advantageous in the molar ratios of 1: 1 to about 10: 1 (1 or 10 parts of di- or polyol) and the forming alcohol and water and the excess component after removed condensation removed by distillation. The target molecule contains alcohol and acid com preferably in the approximate stoichiometric ratio of 1: 1.

The proportion of sulfonic acid-containing acid components is 1 to 99 mol .-%, preferably from 10 to 40, particularly preferably from 15 to 25, mol%, based on the total amount of carboxylic acids.

Very favorable performance properties have the sulfone group-containing Comb polymers of the general formula I, when 1,2-propanediol as diol components and / or diethylene glycol and / or cyclohexanedimethanol, as carboxylic acids isophthalic  acid also with 1,3-cyclohexanedicarboxylic acid or with 2,6-naphthalenedicarboxylic acid acid or with adipic acid and as sulfo-containing radicals 5-sulfoisophthalic acid sodium salt, the sodium salt of isethionic acid are used.

The following is a section of a comb polymer used according to the invention a polyacrylic acid chain is the backbone of the comb polymer molecule forms. The acid functions are esterified with polyols, which in turn with an acid function of Isophthalsäuremolekülen are esterified. Other polyols, from structural elements of this polymer molecule are derived from pentaerythritol, 1,2- Propanediol. As sulfonate group-containing agent, of which structural elements of the Derive, for example, the 5-Sulfoisophthalsäuredialkylester- Na salt.

For reasons of reaction, which are known in the art, prevails in the target polymer no absolute monotony of the substitution, but is to start from a Ge know statistical distribution of the substitution. Furthermore, certain reactive molecular moieties will also be observed to crosslink two or more polymer chains to a more or less complex network, as the following molecular scheme also attempts to do.

The sulfone-containing comb polymers to be used according to the invention are colorless bis yellowish, odorless solids. They are readily soluble in water and alcohols. you  can be advantageously incorporated into cosmetic preparations for strengthening the hair become.

The preparation of inventive comb polymers is advantageously carried out by one or a plurality of polyfunctional alcohols having a sulfonic acid group-containing, at least two substances containing carboxyl groups, for example 5-sulfoisophthalic acid dimethyl ester Na salt, optionally a further at least two carboxyl groups containing substance and a polymer with one or more polycarboxylic acids, For example, polyacrylic acid or polymethacrylic acid combined, heated and be subjected to the usual treatment steps.

In the cosmetic preparations according to the invention, together with the Therefore described comb polymers therefore one or more physiologically compatible anionic and / or amphoteric polymers used as a film former.

In an astonishing way, by choosing the conditions according to the invention, it is possible extremely advantageous product profiles are obtained, or product properties such. B. the Max. Strengthening stage, the curl retention, the reduction of the formation of residue the characteristic of fortification.

In hair sprays, the effects of synergistic effects can be specifically exploited reduced or kept to a minimum by high water content become.

The film-forming anionic or amphoteric polymers used according to the invention re can be beneficial from the group of usual in the field of cosmetics, ins special ingredients used in hair cosmetics are chosen, but also Po For technical applications, such as coating and binder.

Suitable anionic polymers are, for example:
Copolymers of maleic acid, fumaric acid and itaconic acid and the anhydrides and half esters of these acids with vinyl ethers, vinyl esters, vinyl halides, Phenylvinylderi derivatives and acrylic acid and esters thereof, inter alia, from ISP under the trade names GANTREZ® A, SP and ES or OMNIREZ® 2000 are offered.

Particular preference is given here to the type which, according to the INCI nomenclature "Butyl Ester of PVM / MA copolymer ", as described for example under the Handelsbe drawings GANTREZ® Super A-425 is available.

Copolymers of crotonoic acid with vinyl acetate or vinyl propionate and crotonic acid vinyl acetate / vinyl neodecanoate terpolymers prepared according to the INCI nomenclature "VA / Cro tonates / vinyl neodecanoate copolymer ", and those under the Han label names RESYN® from the company National Starch or LUVISET® from the Company BASF are available. Particularly preferred is the type RESYN® 28-2942.

Homo- and copolymers of acrylic and methacrylic acid and the salts of these acids, which with the trade names RETEN® from the company Hercules and VERSICOL® from the company Allied colloid will be offered.

Co- and terpolymers of acrylic or methacrylic acid with ethylene, styrene, vinyl or allyl esters, such as As vinyl acetate, vinyl pyrrolidone or vinyl caprolactam, esters of acrylic and Methacrylic acid with one or more saturated alcohols, which also affect a Po lyalkylenglykol grafted and crosslinked, acrylamide, methacrylamide, N-alkyl and N-hydroxyalkyl substituted acrylic and methacrylamides.

These are u. a. from BASF under the trade names ULTRAHOLD®, LUVIMER® and LUVIFLEX® from National Starch under the name AMPHOMER®, LOVOCRYL®, VERSATYL® and BALANCE®, the company ISP under the name ACRYLIDONE®, ACCUDYNE® or ADVANTAGE PLUS® and American Cyanamide sold under the trade name QUADRAMER®.

Particularly preferred are the types ULTRAHOLD® 8 and Strong (INCI: Acry lates / acrylamide copolymer), LUVIMER® 100P (INCI: Acrylates Copolymer), BALANCE®  0/55 (INCI: Acrylates Copolymer) and ACCUDYNE® 258 (INCI: Acrylates / Hy droxyesteracrylates copolymer).

Polymers which vinylsulfonic, styrenesulfonic, Naphthalinsulfonsäure- or acrylic have amidoalkylsulfonsäureeinheiten, such as. B. salts of Polyacrylamidsulfonsäuren and copolymers of acrylic or methacrylic acid and the esters of these acids and Acrylamide, acrylamide derivatives, vinyl ethers and vinylpyrrolidone, or salts of poly styrenesulfonic acid, the z. B. as sodium salts under the trade name FLEXAN® of the Company National Starch are offered.

Suitable amphoteric polymers are:
Copolymers of N-substituted alkylacrylic or methacrylamides, such as. As N-ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, acids, such as. As acrylic, methacrylic, Cro ton, Itacon-, maleic and fumaric acid and the alkyl esters of these acids and basic units consisting of esters of acrylic or methacrylic acid with primary, secondary ren and tertiary amine substituents or ammonium substituents, such as. B. N-tert-butylaminoethyl methacrylate.

These are sold under the trade names AMPHOMER®, AMPHOMER® LV-71 and BALANCE®-47 offered by the company National Starch, with the type AMPHOMER® LV-71 (INCI: Octylacrylamide / Acrylates / Butylaminoethyl Methacrylate Copolymer) is particularly preferred.

Copolymers of betaine-type dialkylaminoalkyl (meth) acrylates or dialkylaminoethyl (meth) acrylamides available from the companies Mitsubishi Chemical Coop and Clariant under the trade names DIAFORMER® and YUKAFORMER® are offered.

To improve the water solubility or water dispersibility of the anionic and amphoteric polymers can be neutralized with suitable bases. For this purpose, alkali and alkaline earth hydroxides, ammonia and organic amines, especially Amino alcohols, such as. Triethanolamine, tri-propanolamine, 2-amino-2-methyl-1-pro panol, 2-amino-2-methyl-1,3-propanediol alone or in mixtures. Sodium hydroxide and 2-amino-2-methyl-1-propanol are particularly preferred.  The neutralization of the free acid groups can thereby depending on the application part wise or complete, with a degree of neutralization of 80-100% preferred becomes.

The cosmetic preparations according to the invention for strengthening the hair contain the comb polymers in concentrations between 0.5 and 20 wt .-% and the anioni and / or amphoteric polymers in concentrations between 0.5 and 20% by weight, in each case based on the total formulation.

Preference is given here to a total polymer content of max. 20 weight percent, based to the overall formulation, which consists of the proportions of the silicone according to the invention modified comb polymers and the anionic and / or amphoteric polymers composed.

In a particular embodiment of the present invention, the inventions Water-soluble and / or water-dispersible comb poly used according to the invention mers consisting of a polyacrylic acid-containing polymer main chain and sulfone group-containing polyester side arms therefore in cosmetic, especially Haarkosme incorporated table preparations.

For use, the cosmetic and dermatological according to the invention Preparations in the usual way for cosmetics on the hair in sufficient Quantity applied.

The cosmetic and dermatological preparations according to the invention can contain cosmetic excipients, as ver usually in such preparations ver be used, for. As preservatives, bactericides, perfumes, substances for Ver foaming, dyes, pigments having a coloring effect, Ver thickeners, surface-active substances, emulsifiers, softening, anfeuch tende and / or moisturizing substances, fats, oils, waxes or other common Ingredients of a cosmetic or dermatological formulation such as alcohols, Polyols, polymers, foam stabilizers, electrolytes, organic solvents or Silicone derivatives.  

In cosmetic preparations for strengthening the hair, such as. Hair sprays, hair paints, mousse, liquid, styling gels, etc., the present invention to be used comb polymers preferably in concentrations of 0.5 to 30 Ge percent by weight.

The compositions according to the invention for strengthening the hair can be described as Hair sprays or Schaumaerosole present and the usual and the state of the Technique corresponding additions contain, provided appropriate compatibility is present. These are, for example, further solvents such as lower polyalcohols and their toxicologically tolerated ethers and esters, plasticizers, light and heavy volatile silicones, volatile and low volatility branched or unbranched hydrocarbons aerosols, emulsifiers, antioxidants, waxes, stabilizers, pH regulators, Dyes, bodying agents, antistatic agents, UV absorbers, perfumes, etc.

If the composition of the invention as hair spray or foam aerosol ver used, so a blowing agent is usually added. Usual propellants are lower alkanes, for example propane, butane or isobutane, dimethyl ether, nitrogen, Nitrogen dioxide or carbon dioxide or mixtures of these substances.

When used in mechanical spray or foam devices, for example Spray pumps or manual foam pumps or squeeze systems, can Propellants usually omitted.

The aqueous preparations according to the invention may advantageously contain Al alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, Isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or -mo nobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethy glycol monomethyl or monoethyl ether and analogous products, furthermore lower alcohols Riger C number, z. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular a or a plurality of thickening agents, which or which can be selected advantageously from the group silicon dioxide, aluminum silicates, polysaccharides or their derivatives, z. As hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the group of soge named carbopols, for example carbopols of types 980, 981, 1382, 2984, 5984, each individually or in combination.  

In the technical sense are understood by gels: Relatively dimensionally stable, light deformable disperse systems of at least two components, which are usually from a - usually solid - colloid-divided substance from long-chain molecular groupings (eg, gelatin, silicic acid, polysaccharides) as a scaffolding agent and a liquid di spersionsmittel (eg water) exist. The colloidally divided substance is often called Ver thickening or gelling agent called. He forms a spatial network in the Disper single colloidal particles via electrostatic Wech interaction with each other more or less firmly linked. The dispersion The medium that surrounds the network is characterized by its electrostatic affinity Gelling agent, d. h., A predominantly polar (in particular: hydrophilic) gelling agent Preferably, a polar dispersant (especially: water) gels, whereas a predominantly nonpolar gelling agent preferably gels nonpolar dispersant.

Strong electrostatic interactions, for example, in Wasserstoffbrüc kenbindungen between gelling agent and dispersant, but also between Disper can be implemented with each other molecules, too strong networking can also of the dispersant. Hydrogels can be almost 100% water (besides, for example, about 0.2-1.0% of a gelling agent) and quite solid Have consistency. The water content is present in ice-like structural elements, so that gels therefore their name origin [from Latin "gelatum" = "Frozen" on the al chimistic term "gelatina" (16th century) for nhdt. "Gelatin"] quite justice the.

Gels according to the invention usually contain lower C number alcohols, e.g. B. Etha nol, isopropanol, 1,2-propanediol, glycerol and water in the presence of a Ver thickening agent, the oily-alcoholic gels preferably silica or a Aluminum silicate, in aqueous-alcoholic or alcoholic gels, preferably one Polyacrylate is.

In cosmetic and dermatological preparations according to the invention, for example For example, it can also be shampoo, preparations for Blow-drying or tinting, preparations for dyeing, to a hairdressing or Treatment lotion act.  

If appropriate, preparations according to the invention can advantageously be obtained by a Characterize content of surfactants. Surfactants are amphiphilic substances that are organic, unpo can dissolve substances in water. They care, conditioned by their specific Molecular structure with at least one hydrophilic and one hydrophobic moiety, for a reduction of the surface tension of the water, the wetting of the skin, the facilitation of soil removal and solution, a gentle rinse off and - ever as desired - for foam regulation.

The hydrophilic portions of a surfactant molecule are usually polar functional groups, for example -COO ^- , -O-SO ₃ ^2- , -SO ₃ ^- , while the hydrophobic parts are usually nonpolar hydrocarbon radicals. Surfactants are generally classified according to the nature and charge of the hydrophilic part of the molecule. Here four groups can be distinguished:

• - anionic surfactants,
• - cationic surfactants,
• Amphoteric surfactants and
• - nonionic surfactants.

Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In aqueous solution they form negatively charged organic ions in an acidic or neutral medium. Cationic surfactants are almost exclusively characterized by the presence of a quaternary ammonium group. In aqueous solution, they form positively charged organic ions in an acidic or neutral environment. Amphoteric surfactants contain both anionic and cationic groups and behave accordingly in aqueous solution depending on the pH as anionic or cationic surfactants. They have a positive charge in a strongly acidic environment and a negative charge in an alkaline environment. In the neutral pH range, however, they are zwitterionic, as the following example is intended to illustrate:
RNH ₂ ⁺ CH ₂ CH ₂ COOH X ^- (at pH = 2) X ^- = any anion, e.g. B. Cl ^-
RNH ₂ ⁺ CH ₂ CH ₂ COO ^- (at pH = 7)
RNHCH ₂ CH ₂ COO ^- B ⁺ (at pH = 12) B ⁺ = any cation, eg. Na ⁺

Typical of non-ionic surfactants are polyether chains. Form nonionic surfactants no ions in aqueous medium.

A. Anionic surfactants

Advantageously used anionic surfactants are
Acylamino acids (and their salts), such as

• 1. acylglutamates, for example sodium acylglutamate, di-TEA-palmitoylaspartate and Sodium Caprylic / Capric Glutamate,
• 2. Acyl peptides, for example palmitoyl-hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed collagen,
• 3. sarcosinates, for example myristoyl sarcosine, TEA lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
• 4. taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,
• 5. acyl lactylate, lauroyl lactylate, caproyl lactylate
• 6. alaninates

Carboxylic acids and derivatives, such as

• 1. Carboxylic acids, for example lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylenate,
• 2. Ester carboxylic acids, for example, calcium stearoyl lactylate, laureth-6 citrate and Sodium PEG-4 lauramide carboxylate,
• 3. Ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,

Phosphoric acid esters and salts such as DEA-oleth-10-phosphate and Dilaureth-4 phosphate,
Sulfonic acids and salts, such as

• 1. Acyl-isethionates, z. B. sodium / ammonium cocoyl isethionate,
• 2. alkylarylsulfonates,
• 3. alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C _12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
• 4. Sulfosuccinates, for example dioctylsodium sulfosuccinate, disodium laurethsulfo succinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfo succinate

such as
Sulfuric acid esters, such as

• 1. alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C _12-13 pareth sulfate,
• 2. Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.

B. Cationic surfactants

Optionally, cationic surfactants to be used are advantageous

• 1. alkylamines,
• 2. Alkylimidazoles,
• 3. Ethoxylated amines and
• 4. Quaternary surfactants.
• 5. esterquats

Quaternary surfactants contain at least one N-atom containing 4 alkyl or aryl groups covalently linked. This results in a positive charge regardless of the pH. Advantageous are alkyl betaine, alkylamidopropyl betaine and alkyl amidopropyl hydroxy sulfain. The cationic surfactants used according to the invention may further be be selected from the group of quaternary ammonium compounds, esp in particular Benzyltrialkylammoniumchloride or bromides, such as Benzyldime thylstearylammonium chloride, further Alkyltrialkylammoniumsalze, for example Cetyltrimethylammonium chloride or bromide, Alkyldimethylhydroxyethylammo ammonium chlorides or bromides, dialkyl dimethyl ammonium chlorides or bromides, alkyl amide ethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl or Cetylpyrimidinium chloride, imidazoline derivatives and compounds with cationic cha such as amine oxides, for example Alkyldimethylaminoxide or Alkylaminoethyldi methyl amine oxides. In particular, cetyltrimethylammonium salts are advantageous turn.

C. Amphoteric surfactants

Advantageously used amphoteric surfactants

• 1. acyl / dialkylethylenediamine, for example, sodium acylamphoacetate, disodium acyl amphodipropionate, disodium alkyl amphodiacetate, sodium acyl amphohydroxy propylsulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,  
• 2. N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropion acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

D. Nonionic surfactants

Advantageously used nonionic surfactants are

• 1. Alcohols,
• 2. alkanolamides, such as cocamide MEA / DEA / MIPA,
• 3. amine oxides, such as cocoamidopropylamine oxide,
• 4. Esters obtained by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,
• 5. Ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated Esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated alcohols rine, ethoxylated / propoxylated triglyceride esters, ethoxylated propoxylated Lano lin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and alkylpoly glycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.
• 6. sucrose ester, ether
• 7. Polyglycerol esters, diglycerol esters, monoglycerol esters
• 8. Methyl glucose esters, esters of hydroxy acids

It is also advantageous to use a combination of anionic and / or amphoteric surfactants with one or more non-ionic surfactants.

As a rule, in the context of the present invention, the use of anionic, amphoteric and / or nonionic surfactants over the use of cationic preferred surfactants.

The cosmetic and dermatological contain active ingredients and excipients as they üb Licherweise for this type of preparations for hair care and hair treatment ver be used. As auxiliaries are preservatives, surface-active Substan zen, substances for preventing foaming, thickeners, emulsifiers, Fet te, oils, waxes, organic solvents, bactericides, perfumes, dyes or pig mente, whose job it is to do the hair or the cosmetic or dermatological Preparation to dye, Elektroyte, substances against the greasing of the hair.  

Electrolytes in the sense of the present invention are water-soluble alkali metals, am mono-, alkaline-earth (including magnesium) and zinc salts inorganic To understand anions and any mixtures of such salts, being guaranteed must be that these salts by pharmaceutical or cosmetic Unbedenk distinguish it.

The anions used according to the invention are preferably selected from the group chlorides, sulphates and bisulphates, phosphates, hydrogenphosphates and the linear and cyclic oligophosphates as well as the carbonates and hydrogencar carbonates.

Cosmetic preparations which are a shampooing agent are included preferably at least one anionic, nonionic or amphoteric surfactant Substance, or mixtures of such substances in an aqueous medium and Aids, as they are usually used for it. The surface-active sub punch or the mixtures of these substances can be in a concentration between 1 wt .-% and 50 wt .-% in the shampoo.

A cosmetic preparation in the form of a lotion that is not rinsed, esp especially a lotion for inserting the hair, a lotion when blow-drying the hair a hairdressing and conditioning lotion, generally provides an aqueous, alcoholic or aqueous-alcoholic solution and contains the present invention used comb polymers.

The compositions according to the invention optionally contain those in Kos metik usual additives, such as perfume, thickener, dyes, deodorant antimicrobials, lipid-replenishing agents, complexing and sequestration agents, pearlescent agents, plant extracts, vitamins, active substances and the like chen.

The following examples are intended to illustrate the present invention without it limit. All quantities, percentages and percentages are, if not otherwise indicated, on the weight and the total amount or on the total amount weight of the preparations.

(A) Production Examples Production Example 1

reactant Mass (g) isophthalic 265.81 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.96 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,2-propanediol 195.40 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are presented, stirred briefly followed by Natriumcarbo nat and 5-Sulfophthalsäuredimethylester-Na salt, isophthalic acid and Polyacrylic acid registered. Thereafter, it is evacuated twice and rendered inert with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is increased to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 minutes. Then it is aerated with N ₂ and the melt discharged.

Production Example 2

reactant Mole (mmol) 1,3-cyclohexane 132.80 isophthalic 132.91 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.94 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,2-propanediol 195.40 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are presented, stirred briefly and then sodium carbonate and sodium 5-sulfophthalate Na salt, isophthalic acid, Cyclohexanedicarboxylic acid and polyacrylic acid registered. Thereafter, it is evacuated twice and Siert inerti with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is raised to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 minutes. Then it is aerated with N ₂ and the melt discharged.

Production Example 3

reactant Mole (mmol) 2,6-naphthalene 172.95 isophthalic 132.91 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.94 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,2-propanediol 195.40 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are presented, stirred briefly and then sodium carbonate and sodium 5-sulfophthalate Na salt, isophthalic acid, 2,6-Naphthalindicar bonsäure and polyacrylic acid registered. Thereafter, it is evacuated twice and rendered inert with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is raised to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 minutes. Then it is aerated with N ₂ and the melt discharged.

Production Example 4

reactant Mole (mmol) adipic acid 161.80 isophthalic 132.91 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.94 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,2-propanediol 195.40 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are presented, stirred briefly and then sodium carbonate and sodium 5-sulfophthalate Na salt, isophthalic acid, Adipic acid and polyacrylic acid registered. Thereafter, it is evacuated twice and rendered inert with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is increased to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 min. Then it is aerated with N ₂ and the melt discharged.

Production Example 5

reactant Mole (mmol) 1,3-cyclohexane 99.20 isophthalic 66.46 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.94 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,2-propanediol 195.40 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation still 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are presented, stirred briefly and then sodium carbonate and sodium 5-sulfophthalate Na salt, isophthalic acid, 1,3-Cyclohexandicar bonsäure and polyacrylic acid registered. Thereafter, it is evacuated twice and rendered inert with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is raised to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 min. Then it is aerated with N ₂ and the melt discharged.

Production Example 6

reactant Mole (mmol) isophthalic 265.80 5-sulfoisophthalic acid, Na salt 118.49 Isethionic acid, Na salt 10.94 polyacrylic acid * 3.00 sodium 0.60 tetraisopropoxide 0.60 1,4-cyclohexanedimethanol 144.21 1,2-propanediol 119.31 diethylene glycol 166.95 * 2 mol-OH groups, M = 25,000 g / mol equim. COOH group

of preparation

In a 2 l four-necked flask equipped with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, 1,4-cyclohexanedimethanol, 1,2-propanediol, diethylene glycol, the sodium salt of isethionic acid and titanium tetraisopropylate are initially charged, stirred briefly and then sodium carbonate and 5-sulfophthalic acid dimethyl ester are added. Salt, isophthalic acid, and polyacrylic acid registered. Thereafter, it is evacuated twice and Siert inerti with N ₂ . While stirring is then heated to 170 ° C within 30 min. At about 173 ° C, the transesterification or distillation begins. In the course of 2 hours, the internal temperature is raised to 210 ° C, then to 240-250 ° C and condensed for a further 30 min. Subsequently, the pressure is reduced to <1 mbar and condensed for 1 hour at 250 ° C in 30 minutes. Then it is aerated with N ₂ and the melt discharged.

formulation Examples

hairsprays

Examples 1-15

mousse

Examples 16-17

styling gels

Examples 18-19

Claims (8)

1. Combinations

• a) water-soluble and / or water-dispersible comb polymers consisting of a main polymer chain and with this polymer main chain via Estergrup groups linked sulfongruppenhaltigen polyester side arms and
• b) one or more substances selected from the group of physiologically tolerated anionic or amphoteric polymers.

2. Hair cosmetic preparations containing an effective amount of combinations

• a) water-soluble and / or water-dispersible comb polymers consisting of a main polymer chain and with this polymer main chain via Estergrup groups linked sulfongruppenhaltigen polyester side arms and
• b) one or more substances selected from the group of physiologically tolerated anionic or amphoteric polymers.

3. Combinations according to claim 1 or formulations according to claim 2, characterized in that the polymeric backbone of the comb polymers is selected from the group of polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their derivatives such as polyacrylic acid, polymethacrylic acid and their esters (esters of both acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid, maleic anhydride, fumaric acid and polynorborneneic acid. 4. Combinations according to claim 1 or preparations according to claim 2, characterized in that the comb polymers are selected from the group of polyester fol gender generic structural formulas
be selected at p and o so that the average molecular weights of the main chain constituents used are between 200 and 2,000,000 glmol, the range of 2,000-100,000 g / mol preferably being used,
the polyester side chains according to formula I-III advantageously consist of:
G: is selected from the group of at least two terminal oxygen atoms containing aromatic, aliphatic or cycloaliphatic Organyleinhei th with a carbon number of C ₂ to C ₂₂ or derivatives of a polyglycol of the form HO- [R ³ -O) _k - [R ⁴ -O ) _m -H, corresponding to an organyl unit
where the radicals R ³ and R ^{4 are} alkylene radicals having a carbon number of C ₂ -C ₂₂ , where both radicals do not necessarily have to be different,
wherein for the coefficients k and m: k + m ≧ 1, wherein k and m can be further selected so that the previously designated average molecular weights of a set main chain constituents come about.
D: an at least two terminal acyl-containing aromatic, ali phatic or cycloaliphatic organyl moiety having a carbon number of C ₂ to C ₂₂ , wherein combinations of several different acid components can be contained in the claimed target molecule, for example an organyl moiety of the scheme
where R ^{s can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals having carbon numbers of C ₂ to C ₂₂ .
T: a compound from the group of at least two terminal acyl-containing sulfonated aromatic, aliphatic or cycloaliphatic organyl compounds
R ¹ : may mean lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, wherein the alkyl positions of the amines are independently occupied by C ₁ to C ₂₂ alkyl radicals and 0 to 3 hydroxyl groups.
R ² : a molecule residue selected from the groups of

• aromatic, aliphatic or cycloaliphatic amino functions: (-NH-R ⁵ , -NR ⁵ ₂ , where R ^{5 may be} an alkyl or aryl radical with C ₁ to C ₂₂ )
• aromatic, aliphatic or cycloaliphatic monocarboxylic acid groups: (-COOR ⁶ , where R ^{6 represents} an alkyl or aryl radical with C ₁ to C ₂₀₀ )
• - via ether functions bridged aromatic, aliphatic or cycloaliphatic rule organyl radicals: (-OR ⁵ )
• - Via ether functions bridging polyalkoxy compounds of the form
  -O- [R ⁷ -O] _q - [R ⁸ -O] _r -Y
  The radicals R ⁷ and R ⁸ are advantageously alkyl radicals having a carbon number of C ₂ -C ₂₂ , where both radicals do not necessarily have to be different. The radical Y can be both hydrogen and aliphatic with C ₁ -C ₂₂ . For the coefficients q and r: q + r ≧ 1.
• - Via ether functions bridging singly or multiply ethoxylated sulfo-ned organyl or preferably their alkali metal or alkaline earth metal salts, as for example advantageously characterized by the generic structural formula
  - (O-CH ₂ -CH ₂ ) _s -SO ₃ R ¹
  with s ≧ 1, and wherein s can also be chosen so that the pre designated denominated average molecular weights of the main chain components used come about.

5. Combinations according to claim 1 or preparations according to claim 2, characterized ge indicates that the average molecular weights of the comb polymers advantageously between 200 and 2,000,000 g / mol are, particularly advantageously between 200 and 100,000 g / mol with the range of 1,000-30,000 g / mol preferably being used, very particularly advantageous from 5,000 to 15,000 g / mol. 6. Combinations according to claim 1 or preparations according to claim 2, characterized ge indicates that the anionic polymer or polymers are selected from the group Copolymers of maleic acid, fumaric acid and itaconic acid and of anhydrides and Half esters of these acids with vinyl ethers, vinyl esters, vinyl halides, phenylvinylderi and acrylic acid and esters thereof, preferably the type which according to the INCI no "Butyl Ester of PVM / MA Copolymer" is called, copolymers of Crotonen acid with vinyl acetate or vinyl propionate and crotonic acid / vinyl acetate / vinylneode canato terpolymers prepared according to the INCI nomenclature "VA / Crotonates / Vinyl Neo decanoate copolymers ", homo- and copolymers of acrylic and meth acrylic acid and the salts of these acids, copolymers and terpolymers of acrylic or methacrylic acid with ethylene, styrene, vinyl and / or allyl esters, such as. For example, vinyl acetate, vinyl pyrrolidone or vinylcaprolactam, esters of acrylic and methacrylic acid with one or more saturated alcohols which may also be grafted and crosslinked onto a polyalkylene glycol can, acrylamide, methacrylamide, N-alkyl and N-hydroxyalkyl-substituted acrylic and  Methacrylamiden, whereby preferred are the types, which according to the INCI nomenclature "Acrylates / Acrylamide Copolymer" or "Acrylates Copolymer" or "Acrylates / Hy droxyesteracrylates Copolymer ", polymers, the vinylsulfonic acid, Sty sulfonic acid, naphthalenesulfonic acid and / or acrylamidoalkylsulfonic acid units own, such. For example, salts of polyacrylamide sulfonic acids and copolymers of acrylic or methacrylic acid and the esters of these acids and acrylamide, acrylamide derivatives, Vinyl ethers and vinyl pyrrolidone, or salts of polystyrene sulfonic acid. 7. Combinations according to claim 1 or preparations according to claim 2, characterized in that the one or more amphoteric polymers are selected from Group copolymers of N-substituted alkylacrylic or methacrylamides, such as. B. N Ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, acids, such. B. Acry, Methacrylic, crotonic, itaconic, maleic and fumaric acids and the alkyl esters of these acids and basic units consisting of esters of acrylic or methacrylic acid with pri mary, secondary and tertiary amine substituents or ammonium substituents, such as z. For example, N-tert-butylaminoethyl methacrylate, preferably those described by the INCI nomenclature octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, Copolymers of betaine-type dialkylaminoalkyl (meth) acrylates or dialkylaminoethyl (Meth) acrylamides. 8. Combinations according to claim 1 or preparations according to claim 2, characterized ge indicates that the one or more anionic and / or amphoteric polymers with ge suitable bases are neutralized, for example with alkali and alkaline earth hydroxides, Ammonia and organic amines, especially amino alcohols, such as. Triethanolamine, tri isopropanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol alone or in mixtures, preferably sodium hydroxide and 2-amino-2-methyl-1-propanol, depending on the application, partial or complete neutralization can, and wherein a degree of neutralization of 80-100% is preferred.